Hydrogen bonding in the recovery of phenols and methyl-t-butyl ether : molecular modeling and calorimetry

The purification of waste water is very important, for clean potable water is a common good and a necessity. Surface water purification is nowadays carried out on a massive industrial scale, and clean water is at our disposal virtually everywhere and always. However, cleaning industrial waste water can be a difficult task. Although apolar and slightly polar compounds can be removed from water relatively easily e.g. by extraction to an apolar phase, more polar pollutants like phenol and methyl-tert-butyl ether (MTBE), the two main compounds that this thesis deals with, cannot be removed as easily. A more effective method is therefore needed to clean water that is contaminated with either phenol or MTBE. Solvent-Impregnated Resins (SIRs) are porous polymer beads containing apolar organic extractant liquids. They are used as three-phase separation systems. When brought into contact with a SIR, a solute will preferentially partition from the aqueous phase into the impregnated solvent phase. A drawback to the use of solely the organic extraction liquid in SIRs is the limited solubility of more polar compounds like phenols and ethers in such a medium. In order to enhance extraction, complex-forming extractants can be added to the organic solvent. By means of complex formation inside the organic solvent, the overall equilibrium distribution can be shifted towards the SIR, with a concomitant enhancement of the extraction efficiency. A tight binding of the pollutant molecules to the extractant will eventually ensure high distribution coefficients. However, a moderate binding strength would enable a relatively easy regeneration of the complexing agent after a binding event, enabling multiple uses of the same compound. In this thesis hydrogen-bond (H-bond) complexation, a specific and strong yet reversible way of binding is investigated for phenol recovery and MTBE recovery from aqueous environments, involving the use of organic complexing agents that can be used inside the SIR to enhance the extraction. Potentially interesting compounds were investigated on a molecular scale by quantum chemical modeling methods and subsequent synthesis and physical characterization by primarily calorimetric means. H-bond complex formation has been evaluated and the important parameters determining the binding process have been described. After a general introduction in Chapter 1, Chapters 2 through 4 describe phenol complexation by several different classes of complexing agents. In Chapter 2, the binding of phenol and thiophenol by phosphine oxides, phosphates, and their thio-analogs was investigated. Modeling experiments, isothermal titration calorimetry (ITC) measurements, and liquid-liquid extraction experiments showed that, in principle, the binding affinity of the oxide compounds for phenol is high, whereas the sulfide compounds show only low affinity. In particular, the binding behavior of tri-n-octylphosphine oxide towards phenol and a series of electron-withdrawing group (EWG)-substituted phenols was studied, both in the presence and absence of water in the system. It was found that the presence of water in the system – as can be expected in industrial applications – yields lower binding affinities by as much as 60 %, but the binding stoichiometry remained specific and 1 : 1 complexes were still found. Electronic and steric effects were shown to play an important role in phenol binding in the investigated environment. In Chapter 3, these investigations were extended to the modeling of the full homologous series of mono-, di- and tri-substituted phosphine oxides and phosphates and their thio-analogs. Different modeling methods were used to investigate both structural and electronic elements. Dimethylphosphate was found to form the strongest complexes to the investigated phenols, but because this compound forms very strong homo-dimers in solution it cannot be used as an effective extractant. The SCS-MP2 method, that was relatively unexplored for H-bonding until now, was found to yield very accurate energy predictions, whereas the CBS-Q method was found to predict false binding affinities. Solvent effects are shown to immensely influence the binding behavior. Another, even stronger group of H-bond acceptors, amine-N-oxides, was investigated as described in Chapter 4. The binding properties for phenol and thiophenol with three different amine-N-oxides yielded very high binding affinities (up to 30 times higher than for the phosphine oxide compounds). Introduction of EWGs in the amine-N-oxides was shown to yield markedly lower binding affinities towards phenols, providing a handle to fine-tune the interaction and facilitating easier regeneration of the complexing agent in future SIR applications. Solvent effects and the influence of water in the system were investigated, and it was shown that they both influence the phenol binding strength. The results in Chapters 2 through 4 show that phosphates, phosphine oxides, and amine-N-oxides could all be used in future SIR extraction systems, and the choice between these classes of compounds can be made based on more detailed considerations. MTBE binding by several complexing agents was described in Chapter 5. A detailed modeling study of a number of different substituted phenols for MTBE binding was carried out, and the influence of solvents on the binding behavior was investigated, using a.o. the recently developed M06-2X functional and SMD solvent model. The investigated complexing agents were found to show moderate binding affinities to MTBE with binding strengths being closely linked to the acidity of the extractant. Steric effects and a proper consideration of entropic effects are also found to be important to yield successful binding of MTBE. In combination with the existing MTBE distribution coefficient for apolar phases, these moderate binding affinities were found to be able to enhance extraction, in principle, up to the point where it becomes industrially relevant to use such extractants in SIR-based extractions. Finally, in Chapter 6 the performed research is reviewed, and conclusions, recommendations and a wider perspective for future scientific challenges are given. <br/

Search for New Physics in e-e- Scattering

Considering the physics potential of an e-e- collider in the TeV energy range, we indicate a few interesting examples for exotic processes and discuss the standard model backgrounds. Focussing on pair production of weak gauge bosons, we report some illustrative predictions.Comment: 11 LaTeX pages; axodraw.sty and 6 figures included as an uuencoded file; MPI-PhT/94-33 and LMU-09/9

Practical, reliable and inexpensive assay of lycopene in tomato products based on the combined use of light emitting diode (LED) and the optothermal window

Light emitting diode (LED) combined with the concept of optothermal window (OW) is proposed as a new approach (LED-OW) to detect lycopene in a wide range of tomato-based products (tomato juice, tomato ketchup, tomato passata and tomato puree). Phytonutrient lycopene is a dominant antioxidant in these products while beta-carotene is present in significantly lower quantities. Therefore for all practical reasons the interfering effect of beta-carotene at 502 nm analytical wavelength can be neglected. The LED-OW method is low-cost and simple, yet accurate and precise. The major attributes of the new method are its rapid speed of response and the fact that no preparation whatsoever of the sample is needed before the analysis. The lycopene found in tomato products studied here varies from 8 mg/100 g to 60 mg/100 g fresh product. Results obtained by LED-OW method were compared to the outcome of conventional, time consuming spectrophotometric methods and the correlation was very good (R = 0.98). Precision of the LED-OW instrumental setup ranged from 0.5 to 7.4%; the RSD achieved for lycopene-richest samples (= 40 mg/100 g) did not exceed 1.7%. Repeatability of analysis by LED-OW was found to vary between 0.7 and 7.1%

Automated supervised classification of variable stars I. Methodology

The fast classification of new variable stars is an important step in making them available for further research. Selection of science targets from large databases is much more efficient if they have been classified first. Defining the classes in terms of physical parameters is also important to get an unbiased statistical view on the variability mechanisms and the borders of instability strips. Our goal is twofold: provide an overview of the stellar variability classes that are presently known, in terms of some relevant stellar parameters; use the class descriptions obtained as the basis for an automated `supervised classification' of large databases. Such automated classification will compare and assign new objects to a set of pre-defined variability training classes. For every variability class, a literature search was performed to find as many well-known member stars as possible, or a considerable subset if too many were present. Next, we searched on-line and private databases for their light curves in the visible band and performed period analysis and harmonic fitting. The derived light curve parameters are used to describe the classes and define the training classifiers. We compared the performance of different classifiers in terms of percentage of correct identification, of confusion among classes and of computation time. We describe how well the classes can be separated using the proposed set of parameters and how future improvements can be made, based on new large databases such as the light curves to be assembled by the CoRoT and Kepler space missions.Comment: This paper has been accepted for publication in Astronomy and Astrophysics (reference AA/2007/7638) Number of pages: 27 Number of figures: 1

Eliminating the low-mass axigluon window

Using recent collider data, especially on the hadronic width the Z0, we exclude axigluons in the currently allowed low-mass window, namely axigluons in the mass range 50 GeV < M_A < 120 GeV. Combined with hadron collider data from di-jet production, axigluons with masses below roughly 1 TeV are now completely excluded.Comment: 8 pages, no figures, LaTe

Mannitol Reduces the Hydrostatic Pressure in the Proximal Tubule of the Isolated Blood-Perfused Rabbit Kidney during Hypoxic Stress and Improves Its Function

Background/Aims: Hypoxia may play a role in the development of renal failure in donated kidneys. In the present study, the effects of hypoxia on isolated blood-perfused rabbit kidneys were investigated and the effects of mannitol were explored, giving special attention to intratubular pressure. Methods: Kidneys were perfused with their autologous blood during four 30-min periods (P1–P4). P1 was considered baseline function. In P2, hypoxia was induced either alone or with an infusion of mannitol (15 mg/min) during P2–P4. Reoxygenation was applied after P2. Proximal intratubular pressure was measured in all conditions. Results: During hypoxia, renal blood flow doubled and restored immediately in P3. Urine flow stopped in P2, except in the series with mannitol, but gradually resumed in P3 and P4. Likewise, creatinine clearance recovered slightly (50% of P1. Proximal intratubular pressure (mean ± SD) increased from 12 ± 5 in P1 to 24 ± 11 mm Hg during hypoxia and returned to 10 ± 6 mm Hg in P3. This increase was not observed with mannitol. Conclusion: Cellular swelling might be responsible for the suppressed filtration during hypoxia and can be prevented by mannitol

Analysis of MERCATOR data Part I: variable B stars

We re-classified 31 variable B stars which were observed more than 50 times in the Geneva photometric system with the P7 photometer attached to the MERCATOR telescope (La Palma) during its first 3 years of scientific observations. HD89688 is a possible beta Cephei/slowly pulsating B star hybrid and the main mode of the COROT target HD180642 shows non-linear effects. The Maia candidates are re-classified as either ellipsoidal variables or spotted stars. Although the mode identification is still ongoing, all the well-identified modes so far have a degree l = 0, 1 or 2.Comment: 4 pages, 3 figures. To appear in: Proceedings of JENAM 2005 'Distant worlds', Communications in Asteroseismolog

Who violates expectations when? How firms’ growth and dividend reputations affect investors’ reactions to acquisitions

Research summary: We investigate the role of a firm’s dividend and growth reputations in shaping investors’ interpretations of acquisitions as a negative or positive expectation violation. While our findings reveal that both an acquiring firm’s dividend and growth reputations trigger positive investor reactions, they also show that investors react negatively to an acquisition of a target firm with a strong growth reputation when the acquiring firm has a strong dividend reputation. We also find that investors are inclined to give managers “the benefit of the doubt” to the extent that an acquiring firm strategically frames an acquisition announcement in such a way that it provides assurance to investors that the acquisition is meant to exceed investors’ expectations about shareholder value creation. Managerial summary: We study why investors respond to some acquisitions positively and others negatively. We find that the way acquiring and target firms have created shareholder value in the past, and the information conveyed in the acquisition announcements are important determinants of investors’ differential reactions to acquisitions. Our findings show that while investors generally react positively to acquisitions by firms known for creating value either through dividends or growth, their reactions become negative when a firm known for value creation through dividends acquires a target known for value creation through growth. We further find that managers can favorably influence investor reactions by making it salient in the acquisition announcement how the acquisition is intended to exceed investors’ value creation expectations from the acquiring firm