Functionalized surfaces and surface functionalization of nanomaterials

Nature leads, we follow. But nanotechnologists are in hot pursuit, in designing controllable structures that can mimic naturally occurring and artificially synthesized materials on a common platform. The supramolecular chemistry concerns the investigation of nature principles to produce fascinating complexed and functional molecular assemblies, as well as the utilization of these principles to generate novel devices and materials, potentially useful for sensing, catalysis, transport and other applications in medical or engineering science. The work presented in this thesis is a compilation of different synthetic methods to achieve inorganic-organic hybrid nanomaterials. Silicatein, a protein enzyme, which acts both as a catalyst and template for the formation of silica needles in marine sponges, has been used for the biosynthesis of semiconductor metal oxides on surfaces. Silicatein was immobilized on gold (111) surfaces using alkane thiol, as well as on a novel self-assembly of NTA on top of a “cushion” of reactive ester polymer has been successfully employed to make functionalised surfaces. The immobilization of silicatein on surfaces was monitored by surface plasmon spectroscopy, atomic force microscopy and confocal laser scanning microscopy. Surface bound silicatein retains its biocatalytic activity, which was demonstrated by monitoring its hydrocatalytic activity to catalyse the synthesis of biosilica, biotitania, and biozirconia. The synthesis of semiconductor metal oxides was characterized using scanning electron microscopy. This hydrolytic biocatalyst is used to synthesize the gold nanoparticles. The gold nanoparticles are formed by reduction of tetrachloroaurate, AuCl4-, by the action of sulfhydryl groups hidden below the surface groups of the protein. The resulting gold nanoparticles which are stabilized by surface bound silicatein further aggregate to form Au nanocrystals. The shape of the nanocrystals obtained by using recombinant silicatein is controlled through chiral induction by the protein during the nucleation of the nanocrystals. As an extension of this work, TiO2 nanowires were functionalized using polymeric ligand which incorporates the nitrilotriacetic acid (NTA) linker in the back bone to immobilize His-tagged silicatein onto the TiO2 nanowires. The surface bound protein not only retains its original hydrolytic properties, but also acts as a reductant for AuCl4- in the synthesis of hybrid TiO2/silicatein/Au nanocomposites. Functionalized, monocrystalline rutile TiO2 nanorods were prepared from TiCl4 in aqueous solution in the presence of dopamine. The surface bound organic ligand controls the morphology as well as the crystallinity and the phase selection of TiO2. The surface amine groups can be tailored further with functional molecules such as dyes. As an example, this surface functionality is used for the covalent binding of a fluorescent dye,4-chloro-7- nitrobenzylurazene (NBD) to the TiO2 nanorods. The polymeric ligands have been used successfully for the in-situ and post-functionalization of TiO2 nanoparticles. Besides to chelating dopamine anchor group the multifunctional ligand system presented here incorporates a modifier molecule which allows the binding of functional molecules (here the dyes pyrene, NBD, and Texas Red) as well as additional entities which allow tailoring the solubility of inorganic nanocrystals in different solvents. A novel method for the surface functionalization of fullerene-type MoS2 nanoparticles and subsequently binding these nanoparticles onto TiO2 nanowires has been reported using polymeric ligands. The procedure involves the complexation of IF-MoS2 with a combination of Ni2+ via an umbrella-type nitrilotriacetic acid (NTA) and anchoring them to the sidewalls of TiO2 nanowires utilizing the hydroxyl groups of dopamine present in the main contents of polymeric ligand. A convenient method for the synthesis of Au/CdS nanocomposites has been presented, which were achieved through the novel method of thiol functionalization of gold colloids. The thermodynamically most stable phase of ZrO2 (cubic) has been obtained at much lower temperature (180°C). These nanoparticles are highly blue fluorescent, with a high surface area.

Untersuchungen zur Löslichkeit von Kobalt und Eisen in TiO 2-Bulk sowie in TiO 2-Nanoproben und deren Einfluss auf die magnetischen Eigenschaften

Co- und Fe-dotierte Rutil- und Anatas-Bulkproben wurden über einen Sol-Gel Prozess und anschließende thermische Behandlung dargestellt und auf ihre Zugehörigkeit zu der Gruppe der verdünnten magnetischen Oxide untersucht. Die Untersuchungen der dotierten Rutil-Proben mittels Röntgenbeugung, Elektronenmikroskopie und magnetischen Methoden zeigen, dass die Löslichkeit von Co und Fe in der TiO2-Modifikation Rutil sehr gering ist. Oberhalb von 1at% Co bzw. Fe wird neben Rutil die Bildung der Oxide CoTiO3 bzw. Fe2TiO5 beobachtet. Weitere thermische Behandlung im Argon-H2-Strom führte aufgrund der Bildung von metallischem Co bzw. Fe zu einem ferromagnetischen Verhalten. Die TiO2-Modifikation Anatas besitzt eine höhere Löslichkeit, so dass erst oberhalb von 4at% Co bzw. 10at% Fe die Phasen Co3O4 bzw. FeTiO3 neben Anatas auftreten. Entsprechende Proben zeigen ein paramagnetisches Verhalten. Oberhalb der Löslichkeitsgrenze führt die Reduktion im Argon-H2-Strom zu einem ferromagnetischen Verhalten, welches auf metallisches Co bzw. Fe zurückzuführen ist. Analog zu den Bulkproben wurden Co- und Fe-dotierte TiO2-Nanodrähte hergestellt. Das magnetische Verhalten der Fe-dotierten TiO2-Nanodrähte entspricht dem der Fe-dotierten Anatas-Bulkproben. Dagegen führt die Co-Dotierung nicht zu einem Einbau in die TiO2-Nanodrähte, sondern zur Bildung von CoOx-Nanopartikeln. Die entsprechenden Proben zeigen ein schwach ferromagnetisches Verhalten. Dies ist jedoch nicht auf eine ferromagnetische Dotierung der TiO2-Nanodrähte zurückzuführen, sondern auf nicht kompensierte Momente an den Oberflächen der als Verunreinigungen auftretenden CoOx-Nanopartikel. Zusammenfassend wird festgestellt, dass die Löslichkeit von Co und Fe in TiO2 für die Ausbildung eines ferromagnetischen Verhaltens zu gering ist. Der beobachtete Ferromagnetismus lässt sich eindeutig auf magnetische Verunreinigungen zurückführen. Somit können die dotierten TiO2 Proben nicht den verdünnten magnetischen Oxiden zugeordnet werden.

The influence of petrogenetic processes on the composition of Ocean Island Basalts

Ocean Island Basalts (OIB) provide important information on the chemical and physical characteristics of their mantle sources. However, the geochemical composition of a generated magma is significantly affected by partial melting and/or subsequent fractional crystallization processes. In addition, the isotopic composition of an ascending magma may be modified during transport through the oceanic crust. The influence of these different processes on the chemical and isotopic composition of OIB from two different localities, Hawaii and Tubuai in the Pacific Ocean, are investigated here. In a first chapter, the Os-isotope variations in suites of lavas from Kohala Volcano, Hawaii, are examined to constrain the role of melt/crust interactions on the evolution of these lavas. As 187Os/188Os sensitivity to any radiogenic contaminant strongly depend on the Os content in the melt, Os and other PGE variations are investigated first. This study reveals that Os and other PGE behavior change during the Hawaiian magma differentiation. While PGE concentrations are relatively constant in lavas with relatively primitive compositions, all PGE contents strongly decrease in the melt as it evolved through ~ 8% MgO. This likely reflects the sulfur saturation of the Hawaiian magma and the onset of sulfide fractionation at around 8% MgO. Kohala tholeiites with more than 8% MgO and rich in Os have homogeneous 187Os/188Os values likely to represent the mantle signature of Kohala lavas. However, Os isotopic ratios become more radiogenic with decreasing MgO and Os contents in the lavas, which reflects assimilation of local crust material during fractional crystallization processes. Less than 8% upper oceanic crust assimilation could have produced the most radiogenic Os-isotope ratios recorded in the shield lavas. However, these small amounts of upper crust assimilation have only negligible effects on Sr and Nd isotopic ratios and therefore, are not responsible for the Sr and Nd isotopic heterogeneities observed in Kohala lavas. In a second chapter, fractional crystallization and partial melting processes are constrained using major and trace element variations in the same suites of lavas from Kohala Volcano, Hawaii. This inverse modeling approach allows the estimation of most of the trace element composition of the Hawaiian mantle source. The calculated initial trace element pattern shows slight depletion of the concentrations from LREE to the most incompatible elements, which indicates that the incompatible element enrichments described by the Hawaiian melt patterns are entirely produced by partial melting processes. The “Kea trend” signature of lavas from Kohala Volcano is also confirmed, with Kohala lavas having lower Sr/Nd and La/Th ratios than lavas from Mauna Loa Volcano. Finally, the magmatic evolution of Tubuai Island is investigated in a last chapter using the trace element and Sr, Nd, Hf isotopic variations in mafic lava suites. The Sr, Nd and Hf isotopic data are homogeneous and typical for the HIMU-type OIB and confirms the cogenetic nature of the different mafic lavas from Tubuai Island. The trace element patterns show progressive enrichment of incompatible trace elements with increasing alkali content in the lavas, which reflect progressive decrease in the degree of partial melting towards the later volcanic events. In addition, this enrichment of incompatible trace elements is associated with relative depletion of Rb, Ba, K, Nb, Ta and Ti in the lavas, which require the presence of small amount of residual phlogopite and of a Ti-bearing phase (ilmenite or rutile) during formation of the younger analcitic and nephelinitic magmas.

Petrogenesis of dunite, wehrlite and websterite xenoliths from Kimberley, South Africa: Origin as mantle peridotites of cumulates

Dunite, wehrlite and websterite xenoliths occur amongst a large abundance of mantle xenoliths in kimberlites of the Kimberley cluster in South Africa. Up to know they have mostly been neglected. On the basis of texture, major and trace elements, oxygen isotopes as well as Re-Os isotope characteristics, they can be subdivided into two groups. A coarse-grained mantle peridotite group, comprising dunite, wehrlite and websterite xenoliths, that are similar to fertile peridotites and represent upper mantle assemblages that are differently influenced by mantle metasomatism. And a cumulate group, containing fine-grained Fe-rich dunite xenoliths that represent cumulates of flood basalt magmatism related to ~183 Ma Karoo and ~2.7 Ga Ventersdorp events in southern Africa. Dunite, wehrlite and websterite xenoliths have preserved a complex history of melt depletion and metasomatic re-enrichment events, which gives information about the different re-enrichment stages of the subcratonic lithospheric mantle and the spatial differences within the Kaapvaal craton upper mantle. Websterite xenoliths comprise orthopyroxene (40-85 Vol. %), clinopyroxene (5-42 Vol. %), garnet (4-10 Vol. %) and subordinately olivine, while dunite and wehrlite xenoliths contain predominantly olivine (65-100 Vol %) and subordinately orthopyroxene, clinopyroxene and garnet. High melt depletion and a dunitic to harzburgitic protolith composition are reflected by high forsterite (Fo90-92) and high olivine NiO contents (2800-5000 ppm) and high orthopyroxene Mg# (Mg/(Mg+Fe)) of 0.91-0.93. Re-depletion ages of predominantly 2.9 Ga reflect a minimum age of melt depletion. Melt depletion ceased in conjunction with collision of the Kimberley block with the Witwatersrand block ~2.9 Ga ago. Subduction related re-fertilisation of the previously depleted mantle xenoliths is documented by i) amoeboid textured orthopyroxene, clinopyroxene and garnet, which crystallized in schlieren along olivine grain boundaries, ii) high whole-rock SiO2, Al2O3, CaO, TiO2, FeO contents, iii) low oxygen isotope ratios in clinopyroxene and garnet of 4.8-5.4 ‰ and 4.7-5.3 ‰, respectively and iv) trace element compositions of wehrlitic clinopyroxene and garnet in equilibrium with high-pressure partial melts of eclogite. Trace element disequilibrium of orthopyroxene with clinopyroxene and garnet indicates a separate origin for orthopyroxene, on one side as primary mantle orthopyroxene in dunite and wehrlite xenoliths and on the other side as reaction product with Si-rich melts produced by partial melting of eclogite. This reaction triggered replacement of olivine by orthopyroxene in the surrounding mantle and produced the typical Si-rich composition of Kaapvaal mantle peridotites. Partial melting of eclogite at higher temperatures produced a second metasomatic melt with lower SiO2, but higher Al2O3, CaO, FeO, Ti, Zr, Hf and a low oxygen isotope ratio. This melt triggered clinopyroxene and locally garnet and rutile crystallization in percolation veins, replacing olivine and orthopyroxene in the Kaapvaal upper mantle. Additionally, websterite xenoliths have experienced late stage cryptic metasomatism by the host kimberlite melt, changing the trace element composition of clinopyroxene, orthopyroxene and garnet to different extent. Hence websterite and most fertile lherzolite xenoliths have experienced three metasomatic events: i) reaction with high-Si melt, ii) percolation of subduction related silica melt with lower SiO2 content and iii) cryptic metasomatism by kimberlite. In contrast, dunite and wehrlite xenoliths have only experienced the second metasomatic event. They represent mantle lithologies further away from metasomatising agents. The Fe-rich dunites comprise olivine neoblasts with subordinate olivine porphyroclasts and parallel-orientated needles of ilmenite, which may enclose spinel. The lower forsterite and NiO contents of olivine in Fe-rich dunites compared to mantle peridotite xenoliths (Fo87-89 vs. Fo93-95 and 1300-2800ppm vs. 2200-3900 ppm, respectively), rules out a restitic origin. Cr-rich spinels are remnants of the original cumulate mineralogy that survived a late stage metasomatic overprint related to the production of the host kimberlite, producing ilmenite and phlogopite in some samples. Olivine porphyroclasts and neoblasts have different trace element compositions, the latter having high Ti, V, Cr and Ni and low Zn, Zr and Nb contents, indicating contrasting origins for neoblasts and porphyroclasts. The dunites have high 187Os/188Os ratios (0.11-0.15) indicating young (Phanerozoic) model ages for most samples, whereas three samples show isotopic mixtures between Phanerozoic neoblasts and ancient porphyroclastic material. Most Fe-rich dunite xenoliths can be interpreted as cumulates of fractional crystallization of Karoo magmatism, whereas the porphyroclasts are interpreted to be remnants from the much earlier Archaean Ventersdorp magmatism.

Forward modelling of petrological crust-forming processes on the early Earth

Tonalite-trondhjemite-granodiorite (TTG) gneisses form up to two-thirds of the preserved Archean continental crust and there is considerable debate regarding the primary magmatic processes of the generation of these rocks. The popular theories indicate that these rocks were formed by partial melting of basaltic oceanic crust which was previously metamorphosed to garnet-amphibolite and/or eclogite facies conditions either at the base of thick oceanic crust or by subduction processes.rnThis study investigates a new aspect regarding the source rock for Archean continental crust which is inferred to have had a bulk compostion richer in magnesium (picrite) than present-day basaltic oceanic crust. This difference is supposed to originate from a higher geothermal gradient in the early Archean which may have induced higher degrees of partial melting in the mantle, which resulted in a thicker and more magnesian oceanic crust. rnThe methods used to investigate the role of a more MgO-rich source rock in the formation of TTG-like melts in the context of this new approach are mineral equilibria calculations with the software THERMOCALC and high-pressure experiments conducted from 10–20 kbar and 900–1100 °C, both combined in a forward modelling approach. Initially, P–T pseudosections for natural rock compositions with increasing MgO contents were calculated in the system NCFMASHTO (Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–TiO2) to ascertain the metamorphic products from rocks with increasing MgO contents from a MORB up to a komatiite. A small number of previous experiments on komatiites showed the development of pyroxenite instead of eclogite and garnet-amphibolite during metamorphism and established that melts of these pyroxenites are of basaltic composition, thus again building oceanic crust instead of continental crust.rnThe P–T pseudosections calculated represent a continuous development of their metamorphic products from amphibolites and eclogites towards pyroxenites. On the basis of these calculations and the changes within the range of compositions, three picritic Models of Archean Oceanic Crust (MAOC) were established with different MgO contents (11, 13 and 15 wt%) ranging between basalt and komatiite. The thermodynamic modelling for MAOC 11, 13 and 15 at supersolidus conditions is imprecise since no appropriate melt model for metabasic rocks is currently available and the melt model for metapelitic rocks resulted in unsatisfactory calculations. The partially molten region is therfore covered by high-pressure experiments. The results of the experiments show a transition from predominantly tonalitic melts in MAOC 11 to basaltic melts in MAOC 15 and a solidus moving towards higher temperatures with increasing magnesium in the bulk composition. Tonalitic melts were generated in MAOC 11 and 13 at pressures up to 12.5 kbar in the presence of garnet, clinopyroxene, plagioclase plus/minus quartz (plus/minus orthopyroxene in the presence of quartz and at lower pressures) in the absence of amphibole but it could not be explicitly indicated whether the tonalitic melts coexisting with an eclogitic residue and rutile at 20 kbar do belong to the Archean TTG suite. Basaltic melts were generated predominantly in the presence of granulite facies residues such as amphibole plus/minus garnet, plagioclase, orthopyroxene that lack quartz in all MAOC compositions at pressures up to 15 kbar. rnThe tonalitic melts generated in MAOC 11 and 13 indicate that thicker oceanic crust with more magnesium than that of a modern basalt is also a viable source for the generation of TTG-like melts and therefore continental crust in the Archean. The experimental results are related to different geologic settings as a function of pressure. The favoured setting for the generation of early TTG-like melts at 15 kbar is the base of an oceanic crust thicker than existing today or by melting of slabs in shallow subduction zones, both without interaction of tonalic melts with the mantle. Tonalitic melts at 20 kbar may have been generated below the plagioclase stability by slab melting in deeper subduction zones that have developed with time during the progressive cooling of the Earth, but it is unlikely that those melts reached lower pressure levels without further mantle interaction.rn