Effects of C-H stretching excitation on the dynamics of the O(1D) + CHD3 → OH/OD + CD3/CHD2 reaction.

The vibrationally excited reaction O(1D) + CHD3(ν1 = 1) has been investigated by crossed-molecular-beam experiments with a time-sliced velocity map imaging technique. Detailed and quantitative information is extracted on the C-H stretching excitation effects on the reactivity and dynamics of the title reaction, with the help of preparation of C-H stretching excited CHD3 molecules by direct infrared excitation. Experimental results show that the vibrational stretching excitation of the C-H bond almost does not affect the relative contributions between different dynamical pathways for all product channels. For the OH + CD3 product channel, the vibrational energy of the C-H stretching excited CHD3 reagent is channeled exclusively into the vibrational energy of the OH products. The vibrational excitation of the CHD3 reactant changes the reactivities for the ground-state and umbrella-mode-excited CD3 channels very modestly, while it significantly suppresses the corresponding CHD2 channels. For the CHD2(ν1 = 1) channel, the stretching excited C-H bond of the CHD3 molecule acts almost as a pure spectator.

Time-resolved biofilm deformation measurements using optical coherence tomography.

The interaction of shear stress with the biofilm leads to a dynamic deformation, which is related to the structural and material characteristics of biofilms. We show how optical coherence tomography can be used as an imaging technique to investigate the time-resolved deformation on the biofilm mesoscale as well as to estimate mechanical properties of the biofilm. For the first time time-resolved deformation from cross-sectional views of the inner biofilm structure could be shown. Changes in the biofilm structure and rheological properties were calculated from cross sections in real-time and time-lapsed measurements. Heterotrophic biofilms were grown in a flow cell set-up at low shear stress of τw = 0.01 Pa. By applying higher shear stress elastic and viscoelastic behavior of biofilms were quantified. Deformation led to a change in biofilm conformation and allowed to estimate rheological properties. Assuming an ideal wall shear stress calculation, the shear modulus G = 29.7 ± 1.7 Pa and the Young's modulus E = 36.0 ± 2.6 Pa were estimated.

Effect of CH stretching excitation on the reaction dynamics of F + CHD3 → DF + CHD2.

The vibrationally excited reaction of F + CHD3(ν1 = 1) → DF + CHD2 at a collision energy of 9.0 kcal/mol is investigated using the crossed-beams and time-sliced velocity map imaging techniques. Detailed and quantitative information of the CH stretching excitation effects on the reactivity and dynamics of the title reaction is extracted with the help of an accurate determination of the fraction of the excited CHD3 reagent in the crossed-beam region. It is found that all vibrational states of the CHD2 products observed in the ground-state reaction, which mainly involve the excitation of the umbrella mode of the CHD2 products, are severely suppressed by the CH stretching excitation. However, there are four additional vibrational states of the CHD2 products appearing in the excited-state reaction which are not presented in the ground-state reaction. These vibrational states either have the CH stretching excitation retained or involve one quantum excitation in the CH stretching and the excitation of the umbrella mode. Including all observed vibrational states, the overall cross section of the excited-state reaction is estimated to be 66.6% of that of the ground-state one. Experimental results also show that when the energy of CH stretching excitation is released during the reaction, it is deposited almost exclusively as the rovibrational energy of the DF products, with little portion in the translational degree of freedom. For vibrational states of the CHD2 products observed in both ground- and excited-state reactions, the CH stretching excitation greatly suppresses the forward scattered products, causing a noticeable change in the product angular distributions.

Determination of mechanical properties of biofilms by modelling the deformation measured using optical coherence tomography.

The advantage of using non-invasive imaging such as optical coherence tomography (OCT) to asses material properties from deformed biofilm geometries can be compromised by the assumptions made on fluid forces acting on the biofilm. This study developed a method for the determination of elastic properties of biofilms by modelling the biofilm deformation recorded by OCT imaging with poroelastic fluid-structure interaction computations. Two-dimensional biofilm geometries were extracted from OCT scans of non-deformed and deformed structures as a result of hydrodynamic loading. The biofilm geometries were implemented in a model coupling fluid dynamics with elastic solid mechanics and Darcy flow in the biofilm. The simulation results were compared with real deformed geometries and a fitting procedure allowed estimation of the Young's modulus in given flow conditions. The present method considerably improves the estimation of elastic moduli of biofilms grown in mini-fluidic rectangular channels. This superior prediction is based on the relaxation of several simplifying assumptions made in past studies: shear stress is not anymore taken constant over the biofilm surface, total stress including also pressure is accounted for, any biofilm shape can be used in the determinations, and non-linear behavior of mechanical properties can be estimated. Biofilm elastic moduli between 70 and 700 Pa were obtained and biofilm hardening at large applied stress due to increasing flow velocity was quantified. The work performed here opens the way for in-situ determination of other mechanical properties (e.g., viscoelastic properties, relaxation times, plastic yields) and provides data for modelling biofilm deformation and detachment with eventual applications in biofilm control and removal strategies.

Low biosorption of PVA coated engineered magnetic nanoparticles in granular sludge assessed by magnetic susceptibility.

When engineered nanoparticles (ENP) enter into wastewater treatment plants (WWTP) their removal from the water phase is driven by the interactions with the biomass in the biological treatment step. While studies focus on the interactions with activated flocculent sludge, investigations on the detailed distribution of ENP in other types of biomass, such as granulated sludge, are needed to assess their potential environmental pollution. This study employed engineered magnetic nanoparticles (EMNP) coated with polyvinyl alcohol (PVA) as model nanoparticles to trace their fate in granular sludge from WWT. For the first time, magnetic susceptibility was used as a simple approach for the in-situ quantification of EMNP with a high precision (error <2%). Compared to other analytical methods, the magnetic susceptibility requires no sample preparation and enabled direct quantification of EMNP in both the aqueous phase and the granular sludge. In batch experiments granular sludge was exposed to EMNP suspensions for 18 h. The results revealed that the removal of EMNP from the water phase (5-35%) and biosorption in the granular sludge were rather low. Less than 2.4% of the initially added EMNP were associated with the biomass. Loosely bounded to the granular sludge, desorption of EMNP occurred. Consequently, the removal of EMNP was mainly driven by physical co-sedimentation with the biomass instead of sorption processes. A mass balance elucidated that the majority of EMNP were stabilized by particulate organic matter in the water phase and can therefore likely be transported further. The magnetic susceptibility enabled tracing EMNP in complex matrices and thus improves the understanding of the general distribution of ENP in technical as well as environmental systems.