A new instrument for time-resolved static and dynamic light-scattering experiments in turbid media

We present a new 3D cross-correlation instrument that not only allows for static and dynamic scattering experiments with turbid samples but measures at four angles simultaneously. It thus extends the application of cross-correlation light scattering to time-resolved studies where we can, for example, efficiently investigate the temporal evolution of aggregating or phase separating turbid dispersions. The combination of multiangle 3D and on-line transmission measurements is an essential prerequisite for such studies. This not only provides time-resolved information about the overall size and shape of the particles through measurements of the mean apparent radius of gyration and hydrodynamic radius, but also on the weight-average apparent molar mass via the absolute forward scattering intensity. We present an efficient alignment strategy based on the novel design of the instrument and then the application range of the instrument using well-defined model latex suspensions. The effectiveness of the cross-correlation multiangle technique to monitor aggregation processes in turbid suspensions is finally shown for the acidification of skim milk during the yoghurt-making process. Due to the self-assembled nature of the casein micelles an understanding of the sol–gel process induced by the acidification is only feasible if time-resolved light-scattering experiments on an absolute scale are possible under industrially relevant conditions, where the casein solutions are highly turbid

Energy management (Renewable Energy)

Agrarische Roh- und Reststoffe können zur Bereitstellung von Biotreibstoffen für mobile An-wendungen (z.B.: Biodiesel, Biomethan, Bioethanol, …), von Strom und Wärme (z.B.: über Biogasproduktion mit anschließender Verstromung) sowie von Wärme (über Verbrennung) eingesetzt werden. Alternativ kann der Anbau von Feldfrüchten unter Photovoltaikpaneelen erfolgen, welcher eine Mehrfachnutzung des Bodens ermöglicht und zur Entschärfung der Flächenkonkurrenz beiträgt. Die Strategien einer stofflichen und energetischen Nutzung von Ackerfrüchten als Substitut fossiler Rohstoffe stehen teilweise in Konkurrenz zur Lebensmit-telproduktion. In eine nachhaltige Nutzungsstrategie müssen die Biomassepotentiale in Pro-duktionssystemen mit dem Ziel der Erfüllung der 4F (Food, Feed, Fiber and Fuels) genutzt werden.Agricultural raw and waste materials can be used to produce biofuels for transport (e.g. bio-diesel, biomethane, bioethanol, etc.), as well as electricity and heat (e.g. from biogas produc-tion with subsequent combustion in a gas engine, heat from incineration). Alternatively, culti-vating crops under photovoltaic panels allows shared usage of soil and eases land use com-petition. Substituting fossil resources with the material and energetic utilization of crops can-not be achieved without competing with food production. A sustainable utilization strategy must implement the biomass potentials with the goal of fulfilling the 4Fs (food, feed, fiber and fuels)

The pH induced sol-gel transition in skim milk revisited. a detailed study using time-resolved light and X-ray scattering experiments

We present a detailed study of the evolution of the size, structure and stability of casein micelles upon acidification of skim milk typically applied in yogurt-making processes using a combination of time-resolved light and small-angle X-ray scattering experiments. While most of the available light scattering studies on casein acidification have been restricted to transparent and therefore highly diluted samples, we now profit from a newly developed multiangle 3D light scattering instrument, which allows for time-resolved measurements in highly turbid samples. Our experiments clearly demonstrate the presence of two parallel pH-dependent processes, micellar reassembly and aggregation. Using a systematic investigation of the effect of casein concentration, acidification rate, and ionic strength, we are able to decouple these two processes and obtain detailed information about the pH-induced restructuration of the casein micelle structure that occurs prior to destabilization. Moreover, our experiments also unambiguously demonstrate that these micellar reassembly processes are highly concentration dependent, and that typical light scattering studies conducted under highly diluted conditions are resulting in findings that may not be relevant for the situation encountered in industrial processes at higher concentrations. Experiments conducted with covalently cross-linked micelles, where the pH-induced reassembly has been suppressed, further confirm our findings

Structure of β-lactoglobulin microgels formed during heating as revealed by small-angle X-ray scattering and light scattering

We have investigated the structure of microgels formed during heating of demineralized β-lactoglobulin (βlg) solutions at pH 5.9 by small-angle X-ray scattering (SAXS) and light scattering. First, unheated βlg solutions were characterized at different pH values between 2.0 and 7.0. At pH 5.9, βlg solutions contain mainly dimers (with a radius of approx. 2 nm), which coexist with a small number of larger oligomers (approx. 4 nm). Afterwards, βlg microgels, which form upon heating, were studied. They exhibit an average hydrodynamic radius around 130 ± 20 nm and an average molar mass around 7 × 10⁸ g mol⁻¹. We followed the temporal evolution of the various structures that form after different heating times using subsequent SAXS measurements of the entire sample, the soluble fraction where the βlg microgels were removed, and the solvent. After an hour of heating at 85 °C the maximum yield of the βlg microgels (ca. 70%) is almost reached. Interestingly, the SAXS data show a correlation peak corresponding to a characteristic distance of about 9 nm, indicating an internal organization of the microgels. During the heating procedure the pH increases from pH 5.9 to approximately 6.6, which is induced by the partial conversion of βlg into βlg microgels that exhibit less buffering capacity than native protein. The remaining soluble fraction consists of native βlg and some small aggregates, whose number increases on the cost of native βlg as heating time proceeds. We propose that the formation of these lower molecular mass aggregates is triggered by the increased pH

Hydrodynamic Properties of Magnetic Nanoparticles with Tunable Shape Anisotropy: Prediction and Experimental Verification

We describe the characterization of the hydrodynamic properties of anisotropic magnetic nanoparticles using a combination of transmission electron microscopy (TEM) and dynamic as well as depolarized dynamic light scattering (DLS/DDLS). The particles used are nearly monodisperse hematite spindles with an average length of 280 nm and a minor axis of 57 nm, coated with a layer of silica of variable thickness that allows us to tune the particle aspect ratio between 5 and 2. Their geometrical dimensions can thus be determined easily and quantitatively from TEM. Moreover, their size is ideal to employ DLS and DDLS to measure the translational and rotational diffusion coefficients D-T and D-R, while the presence of a magnetic core opens a plethora of opportunities for future studies and applications. We demonstrate that we can successfully predict the hydrodynamic properties of the different particles based on a TEM characterization of their size distribution and using established theoretical models for the hydrodynamic properties of anisotropic particles. When compared with the theoretical predictions, our light scattering measurements are in quantitative agreement. This agreement between theory and experiment is achieved without having to invoke any adjustable free parameter, as the TEM results are used to calculate the corresponding diffusion coefficients on an absolute scale We demonstrate that this is achieved due to a new and simple method for the statistical weighting of the TEM information, and the use of the correct hydrodynamic models for the observed particle shape. In addition, we also demonstrate an enhanced sensitivity of the rotational diffusion for the surface properties of ellipsoidal nanoparticles, and point out that this may serve as an ideal tool toward characterizing functionalized surfaces

An attempt to detect bicontinuity from SANS data

SANS is a powerful tool to characterise microemulsions, which can have a discontinuous droplet-like structure (oil in water (O/W), water in oil (W/O)) or a bicontinuous one. In the present study, we try to distinguish O/W, W/O and bicontinuous microemulsions by SANS measurements under practical conditions and by a certain evaluation technique. For this reason we chose the well characterised ternary system water-non-ionic surfactant (C12E5)-oil (n-octane), at a fixed surfactant concentration and performed SANS measurements throughout its one-phase channel where droplet-like phases as well as bicontinuous phases are well established. We evaluated the scattering data via the 'Generalised Indirect Fourier Transformation' method (GIFT) which is based on a particulate picture. It should therefore give good results in the droplet domains while a poor fit could be expected for the bicontinuous regime. For comparison we also applied the model of Teubner and Strey (TS) which was developed especially for bicontinuous phases, here a bad fit can be expected for the particulate regime. The data evaluation via GIFT leads to relatively good fits throughout the one-phase channel. The results are physically meaningful and are comparable to those of the TS model. We show that the scattering pattern of a bicontinuous microemulsion can be represented by that of a polydisperse particulate system. This is in clear contradiction to the expectation that the particle picture used in the GIFT method must fail when the bicontinuous regime is reached

Improved cooperativity of spin-Labile iron(III) centers by self-assembly in solution

Supramolecular principles have been applied for improving the spin crossover activity of metal centers due to cooperative effects in solution. Thus, incorporation of alkyloxy tails at the phenyl group of Fe(sal₂trien) 2a provides amphiphilic complexes Fe(sal-OR₂trien) 2b−d (b, R = C₆H₁₃; c, R = C₈H₁₇; d, R = C₁₈H₃₇) comprising an apolar group for supramolecular organization and a polar headgroup with potential spin crossover activity due to the presence of a spin-labile iron(III) center. Self-assembly of these complexes in solution resulted in the formation of microsize and submicrosize particles when the alkyl chain was long enough (2d) but not with shorter chains (2a−c). Solutions of 2d showed enhanced spin crossover activity as compared to complexes 2a−c, both in terms of transition temperature and steepness of the transition. This observation has been correlated to an improved cooperativity of the metal centers in 2d due to self-assembly, thus facilitating a tandem spin transition