Enantioselective interactions at the solid-liquid interface of an HPLC column under working conditions

A technique is presented which allows studying the enantioselective interactions occurring at the solid-liquid interface of a chiral stationary phase (CSP) and a racemate relevant to high performance liquid chromatography (HPLC). A conventional chiral column (Chiralpak AS) was mounted on an attenuated total reflection-infrared (ATR-IR) cell mimicking an HPLC setup equipped with an ATR-IR detector. Racemic pantolactone (PL) was used as the selectand. This setup in combination with modulation excitation spectroscopy (MES) allows for the identification of inter- and intramolecular hydrogen bonds being crucial for enantioseparation under HPLC operation conditions. The method is based on a two step strategy. In a first step, the enantiomers are separated by the chiral column similar to a standard HPLC experiment and upon adsorption on the identical CSP deposited on the internal reflection element (IRE), they are detected by ATR-IR spectroscopy. This experiment provides a retention time for each enantiomer. From the difference in retention, a suitable frequency is calculated which is used in a second experiment where the racemate concentration is varied alternately (modulation) in a way that the pulses of ( R)-PL and ( S)-PL exhibit a phase lag of 90 degrees after elution through the column. This procedure allows one to gain separate information of the enantioselective selectand-CSP interaction after performing a demodulation similar to a phase sensitive detection (PSD). A further benefit of this method is the strong enhancement of the signal-to-noise ratio. The effectiveness of the method is demonstrated by investigating the observed faster decrease in retention time of the later-eluted ( R)-PL, as compared to ( S)-PL, when separating at higher temperatures (from 12 to 36 degrees C). The origin is attributed to a weakening of a specific hydrogen bond between the C=O of ( R)-PL and the N-H of the CSP.     

Seeing and Being Seen: The Effects on Gesture Production

Speakers are argued to adapt their language production to their addressee's needs. For instance, speakers produce fewer and smaller hand gestures when interlocutors cannot see each other. Yet is this because speakers know their addressee cannot see them, or because they themselves do not see their addressee? By means of computer‐mediated communication we manipulated these factors independently. We found that speakers took into account what their addressee saw. They produced more and larger gestures when they knew the addressee could see them. Seeing the addressee increased gesture production only if speakers could readily interpret the addressee's eye gaze, which is not usually the case in mediated interaction. Adding this affordance resulted in gesturing being similar in mediated and unmediated communication.     

Metabolomic Differentiation of Brassica rapa Following Herbivory by Different Insect Instars using Two-Dimensional Nuclear Magnetic Resonance Spectroscopy

The metabolic alterations of Brassica rapa (L.) leaves attacked by larvae of the specialist Plutella xylostella L. (Lepidoptera: Yponomeutidae) and the generalist Spodoptera exigua Hubner (Lepidoptera: Noctuidae) were investigated with nuclear magnetic resonance (NMR) spectroscopy, followed by a multivariate data analysis. The principal component analysis (PCA) of ¹H NMR spectra showed that metabolic changes in B. rapa leaves induced by the 2nd and the 4th instars were different from each other. However, the congestion of the one-dimensional ¹H NMR spectrum made it difficult to identify discriminating metabolites. To overcome the spectral complexity, several two-dimensional NMR techniques were applied. Of those evaluated, J-resolved spectroscopy, which affords an additional coupling constant, provided a wide range of structure information on differentiating the metabolites. Based on the J-resolved spectra combined with PCA, the major signals contributing to the discrimination were alanine, threonine, glucose, sucrose, feruloyl malate, sinapoyl malate, and gluconapin.     

Formation and stability of barium aluminate and cerate in NOx storage-reduction catalysts

The formation and stability of BaAl₂O₄ and BaCeO₃ in Pt-Ba/Al₂O₃ and Pt-Ba/CeO₂ based NO_x storage-reduction (NSR) catalysts has been investigated using kinetic measurements, X-ray diffraction, thermal analysis and X-ray absorption spectroscopy. In as-prepared state, the Ba-component in the NSR catalysts was made up of amorphous BaO and BaCO₃. The formation of BaAl₂O₄ started above 850 °C, whereas the formation of BaCeO₃ was already observed at 800 °C and was faster than that of BaAl₂O₄. The stability of BaAl₂O₄ and BaCeO₃ in various liquid and gaseous atmospheres was different. BaAl₂O₄ was rapidly hydrated at room temperature in the presence of water and transformed to Ba(NO₃)₂ and γ-alumina in the presence of HNO₃, whereas BaCeO₃ was decomposed to much lower extent under these conditions. Interestingly, BaCeO₃ was transformed to Ba(NO₃)₂/CeO₂ in the presence of NO₂/H₂O at 300–500 °C. Also, the presence of CO₂ led to decomposition of barium cerate, which has important consequences for the catalyst ageing under NO_x-storage conditions and can be exploited for regeneration of thermally aged NSR-catalysts.     

Teargas,taboo and transformation: A neo-institutional study of community resistance and the struggle to legitimize subway projects in Amsterdam 1960–2018

The last decades have witnessed an increasing prevalence of community resistance against large-scale infrastructure projects that pose serious threats to their environment, calling for further empirical scrutiny. Hence, this paper applies a neo-institutional lens to investigate how project actors who plan and implement large-scale infrastructure projects respond to community resistance in their attempt to legitimize and embed these projects in their environment. To do so, we draw from a longitudinal study of two subway projects in Amsterdam; the East line (1965–1980) and the North-South line (1995-2018). While considered crucial for urban development, both projects encountered severe community resistance by locals protecting the historic city. This resistance, in turn, prompted ‘institutional work’ by project actors to socially (re)construct the projects in pursuit of legitimacy from the Amsterdam community. The twofold contribution of the paper to the field of project studies is (1) the application of a neo-institutional lens showcasing the dynamic interrelation between projects and their environment, processes of institutional transformation, and practices of institutional work; and (2) the longitudinal empirical account exhibiting the contextual dialectic of resistance and accommodation with an emphasis on shifting approaches of institutionalization, the constant struggle to acquire legitimacy, and the local embeddedness of projects.     

The ritualization of transitions in the project life cycle: A study of transition rituals in construction projects

To manage the project life cycle and facilitate transitions, Project Management (PM) research often points to temporal models and structuring devices. However, the social and symbolic facet of transitions in projects remains understudied. Therefore, this research focuses on the ritualization of transitions in projects. Specifically, the aim is to gain insight into the practice and meaning of transition rituals in the project life cycle. To do so we draw from field research in the infrastructure sector where participant-observation was carried out during eight transition rituals in four Dutch construction projects, and 58 interviews were executed with project participants. The contribution to the PM debate on temporary organizing lies in the conceptualization of transition rituals as powerful symbolic and strategic practices in the project life cycle, and in the provision of an overview showcasing how, when and why transition rituals are practiced to facilitate transitions and embed a project in its environment.     

Endothelial repair process and its relevance to longitudinal neointimal tissue patterns: comparing histology with in silico modelling

Re-establishing a functional endothelium following endovascular treatment is an important factor in arresting neointimal proliferation. In this study, both histology (in vivo) and computational simulations (in silico) are used to evaluate neointimal growth patterns within coronary arteries along the axial direction of the stent. Comparison of the growth configurations in vivo and in silico was undertaken to identify candidate mechanisms for endothelial repair. Stent, lumen and neointimal areas were measured from histological sections obtained from eight right coronary stented porcine arteries. Two re-endothelialization scenarios (endothelial cell (EC) random seeding and EC growth from proximal and distal ends) were implemented in silico to evaluate their influence on the morphology of the simulated lesions. Subject to the assumptions made in the current simulations, comparison between in vivo and in silico results suggests that endothelial growth does not occur from the proximal and distal ends alone, but is more consistent with the assumption of a random seeding process. This may occur either from the patches of endothelium which survive following stent implantation or from attachment of circulating endothelial progenitor cells.     

Zur Modellierung von Sauterdurchmesser und Hold-up beim Einsatz eines konischen Turbinenrührers zum Dispergieren gas-flüssig

By comparing the experimental data of the Sauter-mean-diameter d ₃₂ and the hold up ? with models from literature, there are presented equations for d ₃₂ and ? for the used conical turbine in gas-liquid systems. The necessary adjustment of the proportionality constants of the literature equations will be explained on the basis of fluiddynamical phenomena. It can be established by fluid-dynamical results of a former study carried out with laser-doppler-anemometry. Coalescence phenomena are taken into account in the model using an analogy to bubble columns. The analogy to bubble columns turns out to be suitable. Arguments for the necessity of considering the local fluiddynamics in the modelling of dispersions are presented.     

Synthesis and characterization of photoswitchable fluorescent silica nanoparticles

We have designed and synthesized a new functional (amino reactive) highly efficient fluorescent molecular switch (FMS) with a photochromic diarylethene and a rhodamine fluorescent dye. The reactive group in this FMS -N-hydroxysuccinimide ester- allows selective labeling of amino containing molecules or other materials. In ethanolic solutions, the compound displays a large fluorescent quantum yield of 52 % and a large fluorescence modulation ratio (94 %) between two states that may be interconverted with red and near-UV light. Silica nanoparticles incorporating the new FMS were prepared and characterized, and their spectroscopic and switching properties were also studied. The dye retained its properties after the incorporation into the silica, thereby allowing light-induced reversible high modulation of the fluorescence signal of a single particle for up to 60 cycles, before undergoing irreversible photobleaching. Some applications of these particles in fluorescence microscopy are also demonstrated. In particular, subdiffraction images of nanoparticles were obtained, in the focal plane of a confocal microscope.     

Linkage analysis of susceptibility to ozone-induced lung inflammation in inbred mice

Through a survey of all departments of pediatrics, neurology and neuropathology in Germany, we calculated the incidence of all major forms of leukodystrophy. Only diagnoses based on specific biochemical tests in association with typical findings and/or neuroradiologically proven white matter involvement were accepted. In accordance with these strict criteria, 617 cases of leukodystrophy were found (incidence of all forms: app. 2.0/100,000). Minimal incidence was estimated at 0.8/100,000 for adrenoleukodystrophy/adrenomyeloneuropathy (ALD/AMN), 0.6/100,000 for metachromatic leukodystrophy (MLD), and 0.6/100,000 for Krabbe disease. Thus ALD/AMN is apparently underdiagnosed in Germany. A considerable proportion of leukodystrophies could not be classified in spite of adequate diagnostic procedures in experienced centers.