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Eingeladener Vortrag
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Nanoparticles have gained increasing attention in recent years due to their potential and application in different fields including medicine, cosmetics, chemistry, and their potential to enable advanced materials. To effectively understand and regulate the physico-chemical properties and potential adverse effects of nanoparticles, validated measurement procedures for the various properties of nanoparticles need to be developed. While procedures for measuring nanoparticle size and size Distribution are already established, standardized methods for analysis of their surface chemistry are not yet in place, although the influence of the surface chemistry on nanoparticle properties is undisputed. In particular, storage and preparation of nanoparticles for surface analysis strongly influences the analytical results from various methods, and in order to obtain consistent results, sample preparation must be both optimized and standardized. In this contribution, we present, in detail, some standard procedures for preparing nanoparticles for surface analytics. In principle, nanoparticles can be deposited on a suitable substrate from suspension or as a powder. Silicon (Si) Wafers are commonly used as substrate, however, their cleaning is critical to the process. For sample preparation from suspension, we will discuss drop-casting and spin-coating, where not only the cleanliness of the substrate and purity of the suspension but also its concentration play important roles for the success of the preparation methodology.
For nanoparticles with sensitive ligand shells or coatings, deposition as powders is more suitable, although this method requires particular care in fixing the sample.
The paramagnetic ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate [BMIM][FeCl4] was subject to multiple high-precision thermophysical property measurements under both ambient and high pressure. Density rho(p0,T) / kg m-3 and speed of sound u(p0,T) / m s-1 data at ambient pressure were recorded at temperatures T = (278.15 to 343.16) K using a DSA 5000 M combined vibrating tube densimeter and speed of sound analyser with a standard uncertainty of delta rho(p0,T) = ±0.001 kg m-3 and delta u(p0,T) = ±0.1 m s-1, respectively. High-pressure volumetric (p,rho,T) data were measured on an Anton Paar DMA HPM vibrating tube densimeter at T = (273.16 to 413.15) K and at pressures up to p = 140 MPa with an estimated experimental relative combined average percentage deviation (APD) of delta rho(p,T) / rho(p,T) = ±(0.01 to 0.08) %.
The specific isobaric heat capacity cp(p0,T) / J kg-1 K-1, a caloric property, was determined at T = (273.15 to 413.15) K with an uncertainty delta cp / cp = ±0.5 % using a Perkin Elmer Pyris 1 DSC differential scanning calorimeter. To gain knowledge of transport properties, the dynamic viscosity eta(p0,T) / mPa s at ambient pressure was recorded at T = (275.03 to 413.18) K by an Anton Paar SVM 3000 Stabinger viscometer and additionally an Anton Paar rheometer MCR 302 device with uncertainties of delta eta / eta = ±0.35 % and delta eta / eta = ±1 %, respectively.
The obtained data were first correlated by empirical polynomial equations of state and further processed by the application of classic thermodynamic potentials to determine isothermal compressibility kappa T(p,T) / MPa-1, isobaric thermal expansivity alpha p(p,T) / K-1, thermal pressure coefficient gamma(p,T) / MPa K-1, internal pressure pint(p,T) / MPa, specific heat capacity at constant pressure cp(p,T) / J kg-1 K-1 and at constant volume cv(p,T) / J kg-1 K-1, the difference of isobaric and isochoric heat capacity (cp–cv)(p,T) / J kg-1 K-1, speed of sound u(p,T) / m s-1 and ultimately isentropic exponent kappa s(p,T).
This work extends knowledge about the thermophysical properties of [BMIM][FeCl4] particularly to high temperatures and pressures.
Measurements of ion distributions at a charged solid–liquid interface using X-ray standing waves (XSW) are presented. High energy synchrotron radiation (17.48 keV) is used to produce an XSW pattern inside a thin water film on a silicon wafer. The liquid phase is an aqueous solution containing Br and Rb ions. The surface charge is adjusted by titration. Measurements are performed over a pH range from 2.2–9, using the native Si oxide layer and functional (amine) groups as surface charge. The Debye length, indicating the extension of the diffuse layer, could be measured with values varying between 1–4 nm. For functionalized wafers, the pH dependent change from attraction to repulsion of an ion species could be detected, indicating the isoelectric point. In combination with the measurement of the streaming current, the surface charge of the sample could be quantified.
Germination induces the glucosylation of the Fusarium mycotoxin deoxynivalenol in various grains
(2012)
In food, the mycotoxin deoxynivalenol (DON) often occurs in conjunction with its 3-β-D-glucopyranoside (D3G). The transformation of DON to D3G through glucosylation is catalysed by plant enzymes, however, the exact circumstances are not well understood. In order to investigate the role of enzymatic glucosylation in germinating grains, DON treated kernels were steeped and germinated under laboratory conditions. Furthermore, the effect of malting on the DON content of the contaminated barley was investigated. In all cases, DON and its derivatives were quantified by HPLC-MS/MS before, during and after the experiments. Amongst the six tested cereals; wheat, rye, barley, spelt, and millet transformed DON to D3G during germination whilst the oats were inactive. For wheat, barley, and spelt the initial DON content was reduced by 50%, with the loss being almost entirely accounted for by D3G formation. As D3G might be cleaved during digestion, the elevated D3G concentration may obscure the toxicologically relevant DON content in processed food and beer. The germination process has a major influence on the 'masking' of DON, leading to high quantities of D3G that may be missed in common mycotoxin analyses.
In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D-A) substituted 1,2,3-triazoles as conjugative π-linkers between the alkali metal ion receptor N-phenylaza-[18]crown-6 and different fluorophoric groups with different electron-acceptor properties (4-naphthalimide, meso-phenyl-BODIPY and 9-anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge-transfer (CT) type probes 1, 2 and 7, the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge-separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting-up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7, which contains a 9-anthracenyl moiety as the electron-accepting fluorophore, is the only probe which retains light-up features in water and works as a highly K+/Na+-selective probe under simulated physiological conditions. Virtually decoupled BODIPY-based 6 and photoinduced electron transfer (PET) type probes 3–5, where the 10-substituted anthracen-9-yl fluorophores are connected to the 1,2,3-triazole through a methylene spacer, show strong ion-induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3-triazole fluoroionophores.
The production of agglomerate-free SiO2 particles exhibiting a monomodal distribution of particle sizes of around 300 nm by means of direct laser fuming of micrometric SiO2 powders has been successfully demonstrated. With a 12 kW cw CO2 laser system, a production rate of up to 1 kilogram powder per hour was achieved. Almost ideal spherical amorphous SiO2 particles in a broad particle size distribution between 10 nm and several 100 nm (d50 ≈ 300 nm) were synthesized. Several observations suggest weak agglomeration forces between the particles. A temperature reduction of 200 °C for sintering powder compacts was observed.
Bispidines for dual imaging
(2014)
The efficient transformation of the hexadentate bispidinol 1 into carbamate derivatives yields functional bispidines enabling convenient functionalization for targeted imaging. The BODIPY-substituted bispidine 3 combines a coordination site for metal ions, such as radioactive 64CuII, with a fluorescent unit. Product 3 was thoroughly characterized by standard analytical methods, single crystal X-ray diffraction, radiolabeling, and photophysical analysis. The luminescence of ligand 3 was found to be strongly dependent on metal ion coordination: CuII quenches the BODIPY fluorescence, whereas NiII and ZnII ions do not affect it. It follows that, in imaging applications with the positron emitter 64CuII, residues of its origin from enriched 64Ni and the decay products 64NiII and 64ZnII, efficiently restore the fluorescence of the ligand. This allows for monitoring of the emitted radiation as well as the fluorescence signal. The stability of the 64CuII–3 complex is investigated by transmetalation experiments with ZnII and NiII, using fluorescence and radioactivity detection, and the results confirm the high stability of 64CuII–3. In addition, metal complexes of ligand 3 with the lanthanide ions TbIII, EuIII, and NdIII are shown to exhibit emission of the BODIPY ligand and the lanthanide ion, thus enabling dual emission detection.
The present study is dealing with the basic physics for a novel way to generate a free-formed ceramic body, not like common layer by layer, but directly by Selective Volume Sintering (SVS) in a compact block of ceramic powder. To penetrate with laser light into the volume of a ceramic powder compact it is necessary to investigate the light scattering properties of ceramic powders. Compared with polymers and metals, ceramic materials are unique as they offer a wide optical window of transparency. The optical window typically ranges from below 0.3 up to 5 µm wave length. In the present study thin layers of quartz glass (SiO2) particles have been prepared. As a function of layer thickness and the particle size, transmission and reflection spectra in a wave length range between 0.5 and 2.5 µm have been recorded. Depending on the respective particle size and by choosing a proper relation between particle size and wave length of the incident laser radiation, it is found that light can penetrate a powder compact up to a depth of a few millimeters. With an adjustment of the light absorption properties of the compact the initiation of sintering in the volume of the compact is possible.
At the Bundesanstalt für Materialforschung und -prüfung (BAM) full scale specimens for nuclear transport and storage containers (casks) are tested for their structural integrity in a series of drop tests on the Test Site Technical Safety in Horstwalde, 50 km south of Berlin. These drop tests cause a major stress not only on the casks, but also on the steel tower structure of the test facility, itself. The load pattern makes the structure very interesting for detailed investigation. The focus of the monitoring lies on the bolted joints of the flange connections that are a typical connection for cylindrical elements if welding is technical or economical unfavorable. The definition of the monitoring takes was done by investigating the existing documents and inspection results accompanied by building an initial digital representation of the structure, consisting of two finite element (FE) models and a geometrical 3D point cloud representation. As a first step the structures behavior during static and dynamic loading was analyzed using measurement data and an updated numerical FE Model. The idea behind is to use models for a digital planning and operation/evaluation of the structural health monitoring. A static FE simulation and a dynamic FE simulation are generated, to investigate how the structure behaves under the load conditions.
Bulk metallic glasses (BMG) are amorphous metal alloys known for their unique physical and mechanical properties. In the present study, the formation of femtosecond (fs) laser-induced periodic surface structures (LIPSS) on the Zr-based BMGs Zr46Cu46Al8, Zr61Cu25Al12Ti2, Zr52.5Cu17.9Al10Ni14.6Ti5 (Vit105) and Zr57Cu15.4Al10Ni12.6Nb5 (Vit106) was investigated as a function of their different chemical composition. For this purpose, LIPSS were generated on the sample surfaces in an air environment by fs-laser irradiation (λ = 1025 nm, τ = 300 fs, frep = 100 kHz). The surface topography was characterized by scanning electron microscopy and atomic force microscopy. Moreover, the impact of LIPSS formation on the structure and chemical surface composition was analyzed before and after fs-laser irradiation by X-ray diffraction and X-ray photoelectron spectroscopy as well as by transmission electron microscopy in combination with energy dispersive X-ray spectroscopy. Despite the different chemical composition of the investigated BMGs, the fs-laser irradiation resulted in almost similar properties of the generated LIPSS patterns. In the case of Zr61Cu25Al12Ti2, Vit105 and Vit106, the surface analysis revealed the preservation of the amorphous state of the materials during fs-laser irradiation. The study demonstrated the presence of a native oxide layer on all pristine BMGs. In addition, fs-laser irradiation results in the formation of laser-induced oxide layers of larger thickness consisting of an amorphous ZrAlCu-oxide. The precise laser-structuring of BMG surfaces on the nanoscale provides a versatile alternative to thermoplastic forming of BMG surfaces and is of particular interest for the engineering of functional material surfaces.
Reaction monitoring in disperse systems, such as emulsions, is of significant technical importance in various disciplines like biotechnological engineering, chemical industry, food science, and a growing number other technical fields. These systems pose several challenges when it comes to process analytics, such as heterogeneity of mixtures, changes in optical behavior, and low optical activity. Concerning this, online nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for process monitoring in complex reaction mixtures due to its unique direct comparison abilities, while at the same time being non-invasive and independent of optical properties of the sample. In this study the applicability of online-spectroscopic methods on the homogeneously catalyzed hydroformylation system of 1-dodecene to tridecanal is investigated, which is operated in a mini-plant scale at Technische Universität Berlin. The design of a laboratory setup for process-like calibration experiments is presented, including a 500 MHz online NMR spectrometer, a benchtop NMR device with 43 MHz proton frequency as well as two Raman probes and a flow cell assembly for an ultraviolet and visible light (UV/VIS) spectrometer. Results of high-resolution online NMR spectroscopy are shown and technical as well as process-specific problems observed during the measurements are discussed.
The Collaborative Research Center InPROMPT aims to establish a novel process concept for the hydroformylation of long-chained olefins, using a rhodium complex as catalyst in the presence of syngas. Recently, the hydroformylation in micro-emulsions, which allows for the efficient recycling of the expensive rhodium catalyst, was found to be feasible. However, the temperature and concentration sensitive multi-phase system demands a continuous observation of the reaction to achieve an operational and economically feasible plant operation. For that purpose, we tested the potential of both NMR and Raman spectroscopy for process control assistance. The lab-scale experiments were supported by sampling for off-line GC-analysis as reference analytics. The results of the NMR experiments will be part of another contribution.
Hydroformylation represents an important homogeneous catalyzed process, which is widely used within chemical industry. Usually applied with simple alkenes like Propene and Butene aldehydes obtained from alkenes >C6 are relevant intermediates in production of plasticizers, surfactants and polymers. Today the active catalyst species is often based on valuable Rhodium complexes in aqueous solution. This implies the problem of limited water solubility of the reactands, which is acceptable for short chain lengths, but states a problem in case of higher alkenes. Along with that efficient separation and recycling of the catalyst becomes more complicated. There are different approaches tackling this problem, e.g., by using of salt formation in the BASF process or downstream distillation within the Shell process
Confocal micro-X-ray fluorescence (micro-XRF) spectroscopy facilitates three-dimensional (3D) elemental imaging of heterogeneous samples in the micrometer range. Laboratory setups using X-ray tube excitation render the method accessible for diverse research fields but interpretation of results and quantification remain challenging. The attenuation of X-rays in composites depends on the photon energy as well as on the composition and density of the material. For confocal micro-XRF, attenuation severely impacts elemental distribution information, as the signal from deeper layers is distorted by superficial layers. Absorption correction and quantification of fluorescence measurements in heterogeneous composite samples have so far not been reported. Here, an absorption correction approach for confocal micro-XRF combining density information from microcomputed tomography (micro-CT) data with laboratory X-ray absorption spectroscopy (XAS) and synchrotron transmission measurements is presented. The energy dependency of the probing volume is considered during the correction. The methodology is demonstrated on a model composite sample consisting of a bovine tooth with a clinically used restoration material.
Biogenic impact on materials
(2011)
Materials as constituents of products or components of technical systems rarely exist in isolation and many must cope with exposure in the natural world. This chapter describes methods that simulate how a material is influenced through contact with living systems such as microorganisms and arthropods. Both unwanted and desirable interactions are considered. This biogenic impact on materials is intimately associated with the environment to which the material is exposed (Materials-Environment Interaction, Chap. 15). Factors such as moisture, temperature and availability of food sources all have a significant influence on biological systems. Corrosion (Chap. 12) and wear (Chap. 13) can also be induced or enhanced in the presence of microorganisms. Section 14.1 introduces the categories between desired (biodegradation) and undesired (biodeterioration) biological effects on materials. It also introduces the role of biocides for the protection of materials. Section 14.2 describes the testing of wood as a building material especially against microorganisms and insects. Section 14.3 characterizes the test methodologies for two other groups of organic materials, namely polymers (Sect. 14.3.1) and paper and textiles (Sect. 14.3.2). Section 14.4 deals with the susceptibility of inorganic materials such as metals (Sect. 14.4.1), concrete (Sect. 14.4.2) and ceramics (Sect. 14.4.3) to biogenic impact. Section 14.5 treats the testing methodology concerned with the performance of coatings and coating materials. In many of these tests specific strains of organisms are employed. It is vital that these strains retain their ability to utilize/attack the substrate from which they were isolated, even when kept for many years in the laboratory. Section 14.6 therefore considers the importance of maintaining robust and representative test organisms that are as capable of utilizing a substrate as their counterparts in nature such that realistic predictions of performance can be made.
During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed.