Abstract: The discovery of antibiotics represented one of the greatest breakthroughs in medicine. Their success combined with an increasing intensive use is apparently bound to be also their undoing. This is due to the development of acquired antibiotic resistance, leading to inefficient antibiotherapy and even to the impossibility of treatment and death. The development and spread of antibiotic resistance are fueled by the widespread presence of trace levels of antibiotics residue, in various media, from environment to aliments. One of the solutions is the rigorous monitoring of the levels of antibiotics, which in term requires an almost constant development of new, more accessible analytical methods, especially screening methods, capable of decentralized analysis. In this direction, the electrochemical detection of antibiotics represents a very viable alternative. In this context, the aim of this thesis was to develop new electrochemical methods for the detection of antibiotics by employing and expanding on several strategies, like biomimetic sensors and electrochemical fingerprinting. Five studies were described in this thesis, that can be roughly divided in three categories, based on the analytical strategy employed. The first group is represented by direct electrochemical methods. The second group focuses on the use of biomimetic elements, molecularly imprinted polymers and aptamers. The hyphenation of electrochemical methods with other analytical methods was explored in the last group. In the last study, included in this group, the singlet oxygen-based photoelectrochemical approach was used for the detection of a phenolic antibiotic, rifampicin. The originality of the thesis consists in the testing and development of new approaches to various strategies used in electrochemical detection, revealing new insights in the field of electrochemical detection of antibiotics. The complex electrochemical fingerprint and the mechanism of the electrochemical oxidation were created and investigated, respectively, for the antibiotic vancomycin. New sensitive nanoplatforms were prepared by employing and combining new protocols. Additionally, important contributions were brought through the study involving the singlet oxygen-based detection of rifampicin. We demonstrated how a photocatalyst can exhibit analyte selectivity by strongly interacting with a complex phenolic compound, rifampicin. Summing up, the studies presented in this thesis will have an important impact in the field of electrochemical detection of antibiotics.

Abstract: Structured waves are ubiquitous for all areas of wave physics, both classical and quantum, where the wavefields are inhomogeneous and cannot be approximated by a single plane wave. Even the interference of two plane waves, or of a single inhomogeneous (evanescent) wave, provides a number of nontrivial phenomena and additional functionalities as compared to a single plane wave. Complex wavefields with inhomogeneities in the amplitude, phase, and polarization, including topological----- structures and singularities, underpin modern nanooptics and photonics, yet they are equally important, e.g. for quantum matter waves, acoustics, water waves, etc. Structured waves are crucial in optical and electron microscopy, wave propagation and scattering, imaging, communications, quantum optics, topological and non-Hermitian wave systems, quantum condensed-matter systems, optomechanics, plasmonics and metamaterials, optical and acoustic manipulation, and so forth. This Roadmap is written collectively by prominent researchers and aims to survey the role of structured waves in various areas of wave physics. Providing background, current research, and anticipating future developments, it will be of interest to a wide cross-disciplinary audience.

Abstract: Five geothermal waters from the Mons area (southern Belgium) have been studied: one natural hot spring at Stambruges, one stagnant warm water from the inclined tunnels at Baudour, and three thermal waters from the drillholes at St. Ghislain, Ghlin and Douvrain, originating from the carbonate/anhydrite-bearing Visean strata, at depths of ca. 2600, 1550 and 1300 m, respectively. Multielement chemical analysis of the filtered water and its suspended matter > 0.4 μm) was carried out by instrumental neutron activation. Temperature in depth, calculated using the silica (chalcedony) chemical geothermometer, ranged from 75 to 88°C, in good agreement with experimentally determined values. Na/K and Na/K/Ca geothermometers yieilded erratic results, as expected from the geological environment in the aquifer. From the analytical data it can be calculated that the thermal waters of St. Ghislain, Ghlin and Douvrain are not only saturated with respect to chalcedony, but also to anhydrite, calcite, fluorite, barite, strontianite, and possibly zinc silicate, iron (III) hydroxide or siderite, albite, microcline, gibbsite and kaolinite. They are oversaturated with respect to muscovite. Data are also presented for the other thermal waters, and a cold spring water (Claire Fontaine, Stambruges). The similar trace-element composition of the thermal waters can be explained by percolation of the water in the same distant recharge zone, from where it descends, becomes heated at depth and rises along collapse breccia, and locally (Baudour, Stambruges) along fissures. The uptake of higher amounts of Ca, Mg, Sr and sulfate in St. Ghislain and Ghlin, as compared to Douvrain and Baudour is correlated with the boundary between the non-dissolved and dissolved evaporitic zones. This boundary is situated between St. Ghislain and Douvrain, and is roughly parallel with the direction of the groundwater flow (WNW).

Abstract: Het gebruik van plasmon-actieve nanodeeltjes heeft de laatste 10 jaar zeer veel interesse gewekt bij onderzoekers in verschillende toepassingsdomeinen zoals fotokatalyse of oppervlakte versterkte Raman spectroscopie. Er is echter een grote limiterende factor bij het gebruik van edelmetaal nanodeeltjes zoals goud en zilver en dat is de stabiliteit. Deze oxideren en aggregeren snel, zeker in oxidatieve omgeving zoals in lucht. Een interessante aanpak om plasmon-actieve nanodeeltjes te stabiliseren, is om ze te omgeven in een schil, met andere woorden om een kern-schil nanodeeltje te vormen. Er zijn een heel aantal verschillende manieren waarop kern-schil nanodeeltjes gesynthetiseerd kunnen worden. In eerste instantie werden metaal nanodeeltjes omgeven door een (dunne) TiO2 laag. Afhankelijk van de hoeveelheid TiO2 precursor kon de dikte van de laag gecontroleerd worden tot enkele nanometers dik. De stalen werden getest voor de fotokatalytische afbraak van een vaste laag stearinezuur waarbij toevoeging van 2 wt% metaal@TiO2 op P25 leidde tot een significante verbetering in afbraakefficiëntie in vergelijking met zuiver P25. Een andere manier voor het stabiliseren van metaal nanodeeltjes is door ze te omgeven met een polymeerschil. Op deze manier kon de laagdikte gecontroleerd worden met sub-nanometer controle wat een zeer belangrijke factor is voor de hoeveelheid near-field versterking dat buiten de polymeer schil kan gaan. Een XTT test werd uitgevoerd om te bepalen wat de zuurstofactivatie snelheid was van goud en zilver (en goud-zilver bimetallische) nanodeeltjes, al dan niet omgeven door een (niet-)geleidende polymeer laag. Wanneer de stalen gecoat werden met vier niet-geleidende polymeerlagen zakte de zuurstofactivatie nagenoeg tot nul. Aan de andere kant, als goud nanodeeltjes werden omgeven door een geleidende schil was er nog steeds zuurstofactivatie, hoewel lager dan in het geval van goud zonder laag. Het laatste deel van deze thesis focuste meer op mogelijke toepassingen in luchtzuivering. In dit werk werd een glazen buis, gecoat aan de binnenkant met (Ag@polymer gemodificeerd) TiO2, als een spiraal rond een UVA lamp gewikkeld. De geoptimaliseerde spiraalreactor werd dan vergeleken met een conventionele cilindervormige fotoreactor, met dezelfde dimensies en totale katalysatorbelading, over een grote range aan experimentele condities. Uit de resultaten bleek dat de spiraalreactor significant betere afbraakefficiënties vertoonde in vergelijking met de conventionele cilindervormige reactor over een grote range aan debieten. Een adsorptiestap in combinatie met de geoptimaliseerde spiraalreactor zou kunnen leiden tot een zeer krachtige luchtzuiveringstechnologie.

Abstract: Recovery of valuable volatile organic compounds (VOCs) from waste streams is of great industrial importance. Adsorption on zeolites offers an economically and environmentally friendly alternative to conventional activated carbon. When evaluating the suitability of a given zeolite for a particular adsorption application, its adsorption capacity has to be determined. This is traditionally achieved using gas chromatography as an analysis tool, yielding only a few discrete sampling points that constitute the adsorption profile. Meanwhile, only low flow rates and low concentrations of volatile organics can be used, rendering the procedure troublesome and time consuming. Herein, we propose a tool for the fast screening of a large amount of zeolites using on-line and quasi real-time Fourier Transform Infrared Spectroscopy (FTIR). The technique was used to determine the adsorption capacity of three different commercial zeolites and two silica gels, for five industrially relevant VOCs: acetone; methanol; isohexane; isopentane; and toluene. A series of rapid measurements of the individual adsorption capacities were carried out to obtain a detailed overview of the versatility of the proposed method for the characterization of multi-component and multi-sorption bed systems.

Abstract: For the synthesis of gold-silver bimetallic nanoparticles, the Turkevich method has been the state-of-the-art method for several decades. It has been presumed that this procedure results in a homogeneous alloy, although this has been debatable for many years. In this work, it is shown that neither a full alloy, nor a perfect core-shell particle is formed but rather a core-shell-like particle with altering metal composition along the radial direction. In-depth wet-chemical experiments are performed in combination with advanced transmission electron microscopy, including EDX tomography, and Finite Element Method modeling to support the observations. From the electron tomography results, the core-shell structure could be clearly visualized and the spatial distribution of gold and silver atoms could be quantified. Theoretical simulations are performed to demonstrate that even though UV-Vis spectra show only one plasmon band, this still originates from core-shell type structures. The simulations also indicate that the core-shell morphology does not so much affect the location of the plasmon band, but mainly results in significant band broadening. Wet-chemistry experiments provide the evidence that the synthesis pathway starts with gold enriched alloy cores, and later on in the synthesis mainly silver is incorporated to end up with a silver enriched alloy shell.

Abstract: Mechanical deformations and ensuing strain are routinely exploited to tune the band gap energy and to enhance the functionalities of two-dimensional crystals. In this Letter, we show that strain leads also to a strong modification of the exciton magnetic moment in WS2 monolayers. Zeeman-splitting measurements under magnetic fields up to 28.5 T were performed on single, one-layer-thick WS2 microbubbles. The strain of the bubbles causes a hybridization of k-space direct and indirect excitons resulting in a sizable decrease in the modulus of they factor of the ground-state exciton. These findings indicate that strain may have major effects on the way the valley number of excitons can be used to process binary information in two-dimensional crystals.

Abstract: The effects on river water quality of sewer overflows are not well known. Since the duration of the overflow is in the order of magnitude of minutes to hours, continuous measurements of water quality are needed and traditional grab sampling is unable to quantify the pollution loads. The objective of this paper was to demonstrate the applicability of high frequency measurements for assessing the impacts of waste water treatment plants on the water quality of the receiving surface water. In our in situ water quality monitoring setup, two types of multiparameter sensors mounted on a floating fixed platform were used to determine the dynamics of dissolved oxygen, specific conductivity, ammonium-N, nitrate-N and dissolved organic carbon downstream of a waste water treatment plant (WWTP), in combination with data on rainfall, river discharge and WWTP overflow discharge. The monitoring data for water quantity and water quality were used to estimate the pollution load from waste water overflow events and to assess the impact of waste water overflows on the river water quality. The effect of sewer overflow on a small river in terms of N load was shown to be significant. The WWTP overflow events accounted for about 1/3 of the river discharge. The NH4-N loads during overflow events contributed 29% and 21% to the August 2010 and June 2011 load, respectively, in only 8% and 3% of the monthly time span. The results indicate that continuous monitoring is needed to accurately represent the effects of sewer overflows in river systems.