High-velocity transport of nanoparticles through 1-D nanochannels at very large particle to channel diameter ratios

We explore the possibility of generating high-velocity flows of nanoparticles through flat-rectangular nanochannels, which are only 50% deeper than the diameter of the particles. Using the shear-driven flow principle, 200-nm particles can, for example, be transported through a 300-nm-deep channel at velocities up to 35 mm/s (upper limit of our current setup). Working under high-pH conditions, the velocity of the carboxylated nanoparticles still respects the small-molecule velocity law, despite the high degree of confinement to which the particles are subjected. The high degree of confinement is also found to lead to a reduced band broadening. When injecting sharply delimited particle plugs, the plate heights observed for the flow of 0.2-microm particles through a 0.3-microm channel (with plate heights of the order of 1-2 microm) are, for example, approximately 1 order of magnitude smaller than for the flow of 1.0-microm particles through a 1.4-microm channel. It is also found that the band broadening is, within its statistical variation, independent of the fluid velocity over a large range of particle velocities (5-35 mm/s). The flow method distinguishes itself from pressure-driven field-flow fractionation and hydrodynamic chromatography in that the mean particle velocity is independent of the particle size over the entire range of possible particle to channel diameter ratios.     

Importance and reduction of the sidewall-induced band-broadening effect in pressure-driven microfabricated columns

The influence of the detailed design of the sidewall region upon the over-all band-broadening in microfabricated packed-bed or collocated monolithic support structure (COMOSS) columns has been investigated using computational fluid dynamics (CFD) simulation techniques. It is shown that, under unretained solute conditions, very small structural variations of the order of only 5% of the particle diameter can give rise to a 4-fold increase of the band-broadening. A comprehensive study has been made to quantify this effect as a function of the fluid velocity, the particle diameter, the channel widths, and of course, the sidewall region design. Because the sidewall effect can be fully attributed to a mismatch between the flow rates in the column center and in the sidewall region, it is fortunately also quite straightforward to avoid it. A very simple design, yielding band-broadening values identical to that of a hypothetical sidewall-less column for all possible values of the flow velocity, the particle diameter, or the channel width is proposed.     

Stabilization of a chitinase from Serratia marcescens by Gly->Ala and Xxx->Pro mutations

This paper describes attempts to increase the kinetic stabilityof chitinase B from Serratia marcescens (ChiB) by the introductionof semi-automatically designed rigidifying mutations of theGlyAla and XxxPro type. Of 15 single mutants, several displayedsignificant increases in thermal stability, whereas most mutantsshowed minor effects. All mutations with non-marginal effectson stability clustered in a limited, surface-exposed regionof the enzyme, indicating that this region is involved in apartial unfolding process that triggers irreversible thermalinactivation (aggregation). A double mutant containing two stabilizingmutations in this region (G188A, A234P) displayed a 10-foldincrease in half-life at 57°C and a 4.2°C increase inapparent T_m. These results show that entropic stabilizationworks well for ChiB and they pinpoint a region whose unfoldingmay be crucial for the kinetic stability of this enzyme. Received June 18, 2003; revised September 3, 2003; accepted September 12, 2003.     

Using matrix peaks to map topography: increased mass resolution and enhanced sensitivity in chemical imaging

It is well known in secondary ion mass spectrometry (SIMS) that sample topography leads to decreased mass resolution. Specifically, the ion's time of flight is dependent on where it was generated. Here, using matrix-enhanced SIMS, it is demonstrated that, in addition to increasing the yield of intact pseudomolecular ions, the matrix allows the user to semiquantitatively record the topography of a sample. Through mapping the topography-related mass shifts of the matrix (which leads to decreased mass resolution), the analogous mass shifts of higher mass ions can be deconvoluted and higher resolution and greater sensitivity obtained. Furthermore, the semiquantitative topographical map obtained can be compared with any chemical images obtained, allowing the user to quickly ascertain whether local intensity maximums are due to topological features or represent genuine features of interest.     

E. H. Dirksens Beiträge zu den Grundlagen der Analysis

Enno Heeren Dirksen (1788–1850) was one of several mathematicians originating from Eastern Frisia at the end of the eighteenth century to acquire prominence in neohumanist reformed Prussia. While striving—like so many of his contemporaries—for more rigour in the foundations of calculus, his work is significant due to his unusual emphasis on the semiotic aspects of the basic concepts. As a clear-sighted propagator of Cauchy's conceptual innovations in Germany, his achievements in improving sign expressions of such concepts enabled him to clarify hitherto not differentiated multiple limit processes—although less successfully in constructive concept formation itself. The contribution is based on the analysis of Dirksen's published texts and on the numerous texts which remained drafts for his projected voluminousOrganon der gesamten Analysis.

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Menso Folkerts zum 60. Geburtstag gewidmet     

Kristalline und flüssigkristalline copolyester substituierter und unsubstituierter 4-hydroxybenzoesären

Three synthetic strategies were explored to lower the melting point of poly(4-hydroxybenzoate) below 400°C. Binary copolyesters of 4-hydroxybenzoic acid and 3-substituted 4-hydroxybenzoic acid were highly crystalline, regardless of composition, and did not melt below 400°C. In contrast ternary and quartenary copolyesters containing 3-bromo-4-hydroxybenzoic acid may possess melting points below 360°C. Binary copolyesters of 4-mercaptobenzoic acid and 3-substituted 4-hydroxybenzoic acids melt in the range of 360–400°C. Random copolyesters of 3-(4-hydrophenyl) propionic acid and 4-hydroxybenzoic acid are mainly amorphous with glass-transition temperatures between 50 and 15°C. They contain liquid-crystalline domains, which in the case of the 1:1 copolyester are stable over a range of ca. 400°C. The heat-distortion temperatures are low (60–80°C) due to the predominant influence of the amorphous matrix.     

Contaminants, diet, plasma fatty acids and smoking in Greenland 1999-2005

OBJECTIVES: The purpose of this study is to monitor and assess human exposure to pollution in the Arctic which presents a potential future health risk for the local populations. Epidemiological studies in Greenland have shown that human blood levels of several organic contaminants are very high, especially in the North where people depend on local food. In East Greenland (Ittoqqortoormiit (Scoresbysund)) the population shows the highest blood levels of several persistent organic pollutants found in Arctic countries, especially PCB, the levels of which exceed Canadian guideline levels. As in other Arctic countries, the predominant source of these contaminants is the local diet. However, other factors such as smoking may influence the metabolism and thereby the accumulation of toxic substances. STUDY DESIGN: This project is part of the human health program of the ongoing circumpolar "Artic Monitoring and Assessment Programme". Lifestyle, anthropometric factors, and dietary survey results covering 500 men and women from 6 Greenlandic districts were analyzed along with other factors blood lipids, fatty acid profiles, heavy metals and concentrations of persistent organic pollutants (POPs). RESULTS: The dietary survey showed that the traditional food on the average provided 20-30% of the total energy intake. However, the relative monthly meal intake of seal, whale, polar bear, fish and game, and the composition of imported food, varied between districts. Seal and polar bear intake, and, in particular all the plasma n-3 fatty acids, were significantly correlated with organic contaminant concentrations, (betaHCH, chlordanes, DDTs, Hexachlorobenzene, Mirex, PCBs, and toxaphenes) p<0.01(). After adjusting for age, district, dietary factors or plasma n-3 fatty acids, smoking was significantly correlated with high levels of all the above mentioned POPs. CONCLUSION: The main predictors of high contaminant levels in Greenland were age, district, male gender, smoking and high plasma n-3/n-6 ratio as a marker of high dietary intake of local marine mammals.     

Modeling culture in intelligent virtual agents

This work addresses the challenge of creating virtual agents that are able to portray culturally appropriate behavior when interacting with other agents or humans. Because culture influences how people perceive their social reality it is important to have agent models that explicitly consider social elements, such as existing relational factors. We addressed this necessity by integrating culture into a novel model for simulating human social behavior. With this model, we operationalized a particular dimension of culture—individualism versus collectivism—within the context of an interactive narrative scenario that is part of an agent-based tool for intercultural training. Using this scenario we conducted a cross-cultural study in which participants from a collectivistic country (Portugal) were compared with participants from an individualistic country (the Netherlands) in the way they perceived and interacted with agents whose behavior was either individualistic or collectivistic, according to the configuration of the proposed model. In the obtained results, Portuguese subjects rated the collectivistic agents more positively than the Dutch but both countries had a similarly positive opinion about the individualistic agents. This experiment sheds new light on how people from different countries differ when assessing the social appropriateness of virtual agents, while also raising new research questions on this matter.