Speciation of Pu(III) in the environmental system humic substances-groundwater-kaolinite

For the safety assessments of nuclear waste repositories, the possible migration of the radiotoxic waste into environment must be considered. Since plutonium is the major contribution at the radiotoxicity of spent nuclear waste, it requires special care with respect to its mobilization into the groundwater. Plutonium has one of the most complicated chemistry of all elements. It can coexist in 4 oxidation states parallel in one solution. In this work is shown that in the presence of humic substances it is reduced to the Pu(III) and Pu(IV). This work has the focus on the interaction of Pu(III) with natural occurring compounds (humic substances and clay minerals bzw. Kaolinite), while Pu(IV) was studied in a parallel doctoral work by Banik (in preparation). As plutonium is expected under extreme low concentrations in the environment, very sensitive methods are needed to monitor its presence and for its speciation. Resonance ionization mass spectrometry (RIMS), was used for determining the concentration of Pu in environmental samples, with a detection limit of 106- 107 atoms. For the speciation of plutonium CE-ICP-MS was routinely used to monitor the behaviour of Pu in the presence of humic substances. In order to reduce the detection limits of the speciation methods, the coupling of CE to RIMS was proposed. The first steps have shown that this can be a powerful tool for studies of pu under environmental conditions. Further, the first steps in the coupling of two parallel working detectors (DAD and ICP_MS ) to CE was performed, for the enabling a precise study of the complexation constants of plutonium with humic substances. The redox stabilization of Pu(III) was studied and it was determined that NH2OHHCl can maintain Pu(III) in the reduced form up to pH 5.5 – 6. The complexation constants of Pu(III) with Aldrich humic acid (AHA) were determined at pH 3 and 4. the logß = 6.2 – 6.8 found for these experiments was comparable with the literature. The sorption of Pu(III) onto kaolinite was studied in batch experiments and it was determine dthat the pH edge was at pH ~ 5.5. The speciation of plutonium on the surface of kaolinite was studied by EXAFS/XANES. It was determined that the sorbed species was Pu(IV). The influence of AHA on the sorption of Pu(III) onto kaolinite was also investigated. It was determined that at pH < 5 the adsorption is enhanced by the presence of AHA (25 mg/L), while at pH > 6 the adsorption is strongly impaired (depending also on the adding sequence of the components), leading to a mobilization of plutonium in solution.

Synthesis and surface modification of semiconductor nanocrystals

The last decade has witnessed an exponential growth of activities in the field of nanoscience and nanotechnology worldwide, driven both by the excitement of understanding new science and by the potential hope for applications and economic impacts. The largest activity in this field up to date has been in the synthesis and characterization of new materials consisting of particles with dimensions in the order of a few nanometers, so-called nanocrystalline materials. [1-8] Semiconductor nanomaterials such as III/V or II/VI compound semiconductors exhibit strong quantum confinement behavior in the size range from 1 to 10 nm. Therefore, preparation of high quality semiconductor nanocrystals has been a challenge for synthetic chemists, leading to the recent rapid progress in delivering a wide variety of semiconducting nanomaterials. Semiconductor nanocrystals, also called quantum dots, possess physical properties distinctly different from those of the bulk material. Typically, in the size range from 1 to 10 nm, when the particle size is changed, the band gap between the valence and the conduction band will change, too. In a simple approximation a particle in a box model has been used to describe the phenomenon[9]: at nanoscale dimensions the degenerate energy states of a semiconductor separate into discrete states and the system behaves like one big molecule. The size-dependent transformation of the energy levels of the particles is called “quantum size-effect”. Quantum confinement of both the electron and hole in all three dimensions leads to an increase in the effective bandgap of the material with decreasing crystallite size. Consequently, both the optical absorption and emission of semiconductor nanaocrystals shift to the blue (higher energies) as the size of the particles gets smaller. This color tuning is well documented for CdSe nanocrystals whose absorption and emission covers almost the whole visible spectral range. As particle sizes become smaller the ratio of surface atoms to those in the interior increases, which has a strong impact on particle properties, too. Prominent examples are the low melting point [8] and size/shape dependent pressure resistance [10] of semiconductor nanocrystals. Given the size dependence of particle properties, chemists and material scientists now have the unique opportunity to change the electronic and chemical properties of a material by simply controlling the particle size. In particular, CdSe nanocrystals have been widely investigated. Mainly due to their size-dependent optoelectronic properties [11, 12] and flexible chemical processibility [13], they have played a distinguished role for a number of seminal studies [11, 12, 14, 15]. Potential technical applications have been discussed, too. [8, 16-27] Improvement of the optoelectronic properties of semiconductor nanocrystals is still a prominent research topic. One of the most important approaches is fabricating composite type-I core-shell structures which exhibit improved properties, making them attractive from both a fundamental and a practical point of view. Overcoating of nanocrystallites with higher band gap inorganic materials has been shown to increase the photoluminescence quantum yields by eliminating surface nonradiative recombination sites. [28] Particles passivated with inorganic shells are more robust than nanocrystals covered by organic ligands only and have greater tolerance to processing conditions necessary for incorporation into solid state structures or for other applications. Some examples of core-shell nanocrystals reported earlier include CdS on CdSe [29], CdSe on CdS, [30], ZnS on CdS, [31] ZnS on CdSe[28, 32], ZnSe on CdSe [33] and CdS/HgS/CdS [34]. The characterization and preparation of a new core-shell structure, CdSe nanocrystals overcoated by different shells (CdS, ZnS), is presented in chapter 4. Type-I core-shell structures as mentioned above greatly improve the photoluminescence quantum yield and chemical and photochemical stability of nanocrystals. The emission wavelengths of type-I core/shell nanocrystals typically only shows a small red-shift when compared to the plain core nanocrystals. [30, 31, 35] In contrast to type-I core-shell nanocrystals, only few studies have been conducted on colloidal type-II core/shell structures [36-38] which are characterized by a staggered alignment of conduction and valence bands giving rise to a broad tunability of absorption and emission wavelengths, as was shown for CdTe/CdSe core-shell nanocrystals. [36] The emission of type-II core/shell nanocrystals mainly originates from the radiative recombination of electron-hole pairs across the core-shell interface leading to a long photoluminescence lifetime. Type-II core/shell nanocrystals are promising with respect to photoconduction or photovoltaic applications as has been discussed in the literature.[39] Novel type-II core-shell structures with ZnTe cores are reported in chapter 5. The recent progress in the shape control of semiconductor nanocrystals opens new fields of applications. For instance, rod shaped CdSe nanocrystals can enhance the photo-electro conversion efficiency of photovoltaic cells, [40, 41] and also allow for polarized emission in light emitting diodes. [42, 43] Shape control of anisotropic nanocrystals can be achieved by the use of surfactants, [44, 45] regular or inverse micelles as regulating agents, [46, 47] electrochemical processes, [48] template-assisted [49, 50] and solution-liquid-solution (SLS) growth mechnism. [51-53] Recently, formation of various CdSe nanocrystal shapes has been reported by the groups of Alivisatos [54] and Peng, [55] respectively. Furthermore, it has been reported by the group of Prasad [56] that noble metal nanoparticles can induce anisotropic growth of CdSe nanocrystals at lower temperatures than typically used in other methods for preparing anisotropic CdSe structures. Although several approaches for anisotropic crystal growth have been reported by now, developing new synthetic methods for the shape control of colloidal semiconductor nanocrystals remains an important goal. Accordingly, we have attempted to utilize a crystal phase control approach for the controllable synthesis of colloidal ZnE/CdSe (E = S, Se, Te) heterostructures in a variety of morphologies. The complex heterostructures obtained are presented in chapter 6. The unique optical properties of nanocrystals make them appealing as in vivo and in vitro fluorophores in a variety of biological and chemical investigations, in which traditional fluorescence labels based on organic molecules fall short of providing long-term stability and simultaneous detection of multiple emission colours [References]. The ability to prepare water soluble nanocrystals with high stability and quantum yield has led to promising applications in cellular labeling, [57, 58] deep-tissue imaging, [59, 60] and assay labeling [61, 62]. Furthermore, appropriately solubilized nanocrystals have been used as donors in fluorescence resonance energy transfer (FRET) couples. [63-65] Despite recent progress, much work still needs to be done to achieve reproducible and robust surface functionalization and develop flexible (bio-) conjugation techniques. Based on multi-shell CdSe nanocrystals, several new solubilization and ligand exchange protocols have been developed which are presented in chapter 7. The organization of this thesis is as follows: A short overview describing synthesis and properties of CdSe nanocrystals is given in chapter 2. Chapter 3 is the experimental part providing some background information about the optical and analytical methods used in this thesis. The following chapters report the results of this work: synthesis and characterization of type-I multi-shell and type-II core/shell nanocrystals are described in chapter 4 and chapter 5, respectively. In chapter 6, a high–yield synthesis of various CdSe architectures by crystal phase control is reported. Experiments about surface modification of nanocrystals are described in chapter 7. At last, a short summary of the results is given in chapter 8.

Die Rolle von Chemokinrezeptor CXCR4 und Connective Tissue Growth Factor innerhalb der Tumor-Stroma-Interaktion in der akuten myeloischen Leukämie

Die akute myeloische Leukämie (AML) ist eine heterogene Erkrankung der hämatopoetischen Vorläuferzelle, die durch unkontrollierte Vermehrung und ein reduziertes Differenzierungsverhalten gekennzeichnet ist. Aufgrund von Therapieresistenzen und häufig vorkommenden Rückfällen ist die AML mit einer schlechten Langzeitprognose verbunden. Neue Studienergebnisse zeigen, dass leukämische Zellen einer hierarchischen Ordnung unterliegen, an deren Spitze die leukämische Stammzelle (LSC) steht, welche den Tumor speist und ähnliche Charakteristika besitzt wie die hämatopoetische Stammzelle. Die LSC nutzt den Kontakt zu Zellen der hämatopoetischen Nische des Knochenmarks, um die erste Therapie zu überdauern und Resistenzen zu erwerben. Neue Therapieansätze versuchen diese Interaktion zwischen leukämischen Zellen und supportiv wirkenden Stromazellen anzugreifen. rnrnIn dieser Arbeit sollte die Bedeutung des CXC-Motiv Chemokinrezeptors Typ 4 (CXCR4) und des Connective Tissue Growth Factors (CTGF) innerhalb der AML-Stroma-Interaktion untersucht werden. CXCR4, der in vivo dafür sorgt, dass AML-Zellen in der Nische gehalten und geschützt werden, wurde durch den neuwertigen humanen CXCR4-spezifischen Antikörper BMS-936564/MDX-1338 in AML-Zelllinien und Patientenzellen in Zellkulturversuchen blockiert. Dies induzierte Apoptose sowie Differenzierung und führte in Kokulturversuchen zu einer Aufhebung des Stroma-vermittelten Schutzes gegenüber der Chemotherapie. Für diese Effekte musste teilweise ein sekundärer Antikörper verwendet werden, der die CXCR4-Moleküle miteinander kreuzvernetzt.rnDie Auswertung eines quantitativen Real time PCR (qPCR)-Arrays ergab, dass CTGF in der AML-Zelllinie Molm-14 nach Kontakt zu Stromazellen hochreguliert wird. Diese Hochregulation konnte in insgesamt drei AML-Zelllinien sowie in drei Patientenproben in qPCR- und Western Blot-Versuchen bestätigt werden. Weitere Untersuchungen zeigten, dass diese Hochregulation (i) unabhängig von der Stromazelllinie ist, (ii) den direkten Kontakt zum Stroma benötigt und (iii) auch unter hypoxischen Bedingungen, wie sie innerhalb des Knochenmarks vorherrschen, stattfindet. Der durch Zell-Zell- oder Zell-Matrix-Kontakt gesteuerte Hippo-Signalweg konnte aus folgenden Gründen als möglicher upstream-Regulationsmechanismus identifiziert werden: (i) Dessen zentraler Transkriptions-Kofaktor TAZ wurde in kokultivierten Molm-14-Zellen stabilisiert, (ii) der shRNA-gesteuerte Knockdown von TAZ führte zu einer reduzierten CTGF-Hochregulation, (iii) CTGF wurde in Abhängigkeit von der Zelldichte reguliert, (iv) Cysteine-rich angiogenic inducer 61 (Cyr61), ein weiteres Zielgen von TAZ, wurde in kokultivierten AML-Zellen ebenfalls verstärkt exprimiert. Der Knockdown von CTGF führte in vitro zu einer partiellen Aufhebung der Stroma-vermittelten Resistenz und die Blockierung von CTGF durch den Antikörper FG-3019 wirkte im AML-Mausmodell lebensverlängernd. rn rnDie Rolle von CTGF in der AML ist bisher nicht untersucht. Die vorliegenden Ergebnisse zeigen, dass CTGF ein interessantes Therapieziel in der AML darstellt. Es bedarf weiterer Untersuchungen, um die Bedeutung von CTGF in der Tumor-Stroma-Interaktion näher zu charakterisieren und nachgeschaltete Signalwege zu identifizieren.