Mikrostrukturierte Sensoren für die pH-Wert-Bestimung auf Basis von dünnen, intrinisch leitfähigen Polyanilinschichten

Der pH-Wert stellt in der Chemie, Physik, Biologie, Pharmazie und Medizin eine wichtige Meßgröße dar, da eine Vielzahl von Reaktionen durch den pH-Wert bestimmt wird. In der Regel werden zur pH-Wert-Messung Glaselektroden eingesetzt. Hierbei konnte der pH-sensitive Bereich zwar bis auf einige Mikrometer reduziert werden, aber die Gesamtab-messungen betragen immer noch 15-20 cm. Mit der Einführung miniaturisierter Reaktionsgefäße ist daher der Bedarf an miniaturisierten Sensoren enorm gestiegen. Um in solchen Gefäßen Reaktionsparameter wie z. B. den pH-Wert zu kontrollieren, müssen die Gesamtabmessungen der Sensoren verringert werden. Dies lässt sich mit Hilfe der Mikrostrukturtechnik von Silizium realisieren. Hiermit lassen sich Strukturen und ganze Systeme bis in den Nanometerbereich herstellen. Basierend auf Silizium und Gold als Elektrodenmaterial wurden im Rahmen dieser Arbeit verschiedene Interdigitalstrukturen hergestellt. Um diese Strukturen zur pH-Wert-Messungen einsetzen zu können, müssen sie mit einer pH-sensitiven Schicht versehen werden. Hierbei wurde Polyanilin, ein intrinsisch leitendes Polymer, aufgrund seine pH-abhängigen elektrischen und optischen Verhaltens eingesetzt. Die Beschichtung dieser Sensoren mit Polyanilin erfolgte vorwiegend elektrochemisch mit Hilfe der Zyklovoltammetrie. Neben der Herstellung reiner Polyanilinfilme wurden auch Kopolymerisationen von Anilin und seinen entsprechenden Aminobenzoesäure- bzw. Aminobenzensulfonsäurederivaten durchgeführt. Ergebnisse dazu werden vorgestellt und diskutiert. Zur Charakterisierung der resultierenden Polyanilin- und Kopolymerfilme auf den Inter-digitalstrukturen wurden mit Hilfe der ATR-FT-IR-Spektroskopie Spektren aufgenommen, die gezeigt und diskutiert werden. Eine elektrochemische Charakterisierung der Polymere erfolgte mittels der Zyklovoltammetrie. Die mit Polyanilin bzw. seinen Kopolymeren beschichteten Sensoren wurden dann für Widerstandsmessungen an den Polymerfilmen in wässrigen Medien eingesetzt. Polyanilin zeigt lediglich eine pH-Sensitivität in einem pH-Bereich von pH 2 bis pH 4. Durch den Einsatz der Kopolymere konnte dieser pH-sensitive Bereich jedoch bis zu einem pH-Wert von 10 ausgeweitet werden. Zur weiteren Miniaturisierung der Sensoren wurde das Konzept der interdigitalen Elektroden-paare auf Cantilever übertragen. Die pH-sensitive Zone konnte dabei auf 500 µm2 bei einer Gesamtlänge des Sensors (Halter mit integriertem Cantilever) von 4 mm reduziert werden. Neben den elektrischen pH-abhängigen Eigenschaften können auch die optischen Eigen-schaften des Polyanilins zur pH-Detektion herangezogen werden. Diese wurden zunächst mit Hilfe der UV-VIS-Spektroskopie untersucht. Die erhaltenen Spektren werden gezeigt und kurz diskutiert. Mit Hilfe eines Raster-Sonden-Mikroskops (a-SNOM, Firma WITec) wurden Reflexionsmessungen an Polyanilinschichten durchgeführt. Zur weiteren Miniaturisierung wurden Siliziumdioxidhohlpyramiden (Basisfläche 400 µm2) mit Spitzenöffnungen in einem Bereich von 50-150 nm mit Polyanilin beschichtet. Auch hier sollten die optischen Eigenschaften des Polyanilins zur pH-Wert-Sensorik ausgenutzt werden. Es werden erste Messungen an diesen Strukturen in Transmission diskutiert.

Root-induced increases in soil pH and nutrient availability to field-grown cereals and legumes on acid sandy soils of Sudano-Sahelian West Africa

A field experiment with millet (Pennisetum glaucum L.), sorghum [Sorghum bicolor (L.) Moench], cowpea (Vigna unguiculata L.) and groundnut (Arachnis hypogeae L.) was conducted on severely P-deficient acid sandy soils of Niger, Mali and Burkina Faso to measure changes in pH and nutrient availability as affected by distance from the root surface and by mineral fertiliser application. Treatments included three rates of phosphorus (P) and four levels of nitrogen (N) application. Bulk, rhizosphere and rhizoplane soils were sampled at 35, 45 and 75 DAS in 1997 and at 55 and 65 DAS in 1998. Regardless of the cropping system and level of mineral fertiliser applied, soil pH consistently increased between 0.7 and two units from the bulk soil to the rhizoplane of millet. Similar pH gradients were observed in cowpea, but pH changes were much smaller in sorghum with a difference of only 0.3 units. Shifts in pH led to large increases in nutrient availability close to the roots. Compared with the bulk soil, available P in the rhizoplane was between 190 and 270% higher for P-Bray and between 360 and 600% higher for P-water. Exchangeable calcium (Ca) and magnesium (Mg) levels were also higher in the millet rhizoplane than in the bulk soil, whereas exchangeable aluminium (Al) levels decreased with increasing pH close to the root surface. The results suggest an important role of root-induced pH increases for crops to cope with acidity-induced nutrient deficiency and Al stress of soils in the Sudano-Sahelian zone of West Africa.

Structural characterization and distribution of zebrafish germ plasm during interphase and mitosis

In zebrafish, germ cells are responsible for transmitting the genetic information from one generation to the next. During the first cleavages of zebrafish embryonic development, a specialized part of the cytoplasm known as germ plasm, is responsible of committing four blastomeres to become the progenitors of all germ cells in the forming embryo. Much is known about how the germ plasm is spatially distributed in early stages of primordial germ cell development, a process described to be dependant on microtubules and actin. However, little is known about how the material is inherited after it reorganizes into a perinuclear location, or how is the symmetrical distribution regulated in order to ensure proper inheritance of the material by both daughter cells. It is also not clear whether there is a controlled mechanism that regulates the number of granules inherited by the daughter cells, or whether it is a random process. We describe the distribution of germ plasm material from 4hpf to 24hpf in zebrafish primordial germ cells using Vasa protein as marker. Vasa positive material appears to be conglomerate into 3 to 4 big spherical structures at 4hpf. While development progresses, these big structures become smaller perinuclear granules that reach a total number of approximately 30 at 24hpf. We investigated how this transformation occurs and how the minus-end microtubule dependent motor protein Dynein plays a role in this process. Additionally, we describe specific colocalization of microtubules and perinuclear granules during interphase and more interestingly, during all different stages of cell division. We show that distribution of granules follow what seems to be a regulated distribution: during cells division, daughter cells inherit an equal number of granules. We propose that due to the permanent colocalization of microtubular structures with germinal granules during interphase and cell division, a coordinated mechanism between these structures may ensure proper distribution of the material among daughter cells. Furthermore, we show that exposure to the microtubule-depolymerizing drug nocodazole leads to disassembly of the germ cell nuclear lamin matrix, chromatin condensation, and fusion of granules to a big conglomerate, revealing dependence of granular distribution on microtubules and proper nuclear structure.

Relativistic effects in physics and chemistry of element 105. [Part] I.

A detailed study of the electronic structure and bonding of the pentahalides of group 5 elements V, Nb, Ta, and element 105, hahnium (and Pa) has been carried out using relativistic molecular cluster Dirac-Slater discrete-variational method. A number of calculations have been performed for different geometries and molecular bond distances. The character of the bonding has been analyzed using the Mulliken population analysis of the molecular orbitals. It is shown that hahnium is a typical group 5 element. In a great number of properties it continues trends in the group. Some peculiarities in the electronic structure of HaCl_5 result from relativistic effects.

Relativistic effects in physics and chemistry of element 105. [Part] II.

Relativistic self-consistent charge Dirac-Slater discrete variational method calculations have been done for the series of molecules MBr_5, where M = Nb, Ta, Pa, and element 105, Ha. The electronic structure data show that the trends within the group 5 pentabromides resemble those for the corresponding pentaclorides with the latter being more ionic. Estimation of the volatility of group 5 bromides has been done on the basis of the molecular orbital calculations. According to the results of the theoretical interpretation HaBr_5 seems to be more volatile than NbBr_5 and TaBr_5.

Relativistic effects in physics and chemistry of element 105. [Part] III.

Electronic structures of MOCl_3 and MOBr_3 molecules, where M = V, Nb, Ta, Pa, and element 105, hahnium, have been calculated using the relativistic Dirac-Slater discrete variational method. The character of bonding has been analyzed using the Mulliken population analysis of the molecular orbitals. It was shown that hahnium oxytrihalides have similar properties to oxytrihalides of Nb and Ta and that hahnium has the highest tendency to form double bond with oxygen. Some peculiarities in the electronic structure of HaOCl_3 and HaOBr_3 result from relativistic effects. Volatilities of the oxytrihalides in comparison with the corresponding pentahalides were considered using results of the present calculations. Higher ionic character and lower covalency as well as the presence of dipole moments in MOX_3 (X = Cl, Br) molecules compared to analogous MX_5 ones are the factors contributing to their lower volatilities.

Relativistic effects in physics and chemistry of element 105. [Part] IV.

Results of relativistic (Dirac-Slater and Dirac-Fock) and nonrelativistic (Hartree-Fock-Slater) atomic and molecular calculations have been compared for the group 5 elements Nb, Ta, and Ha and their compounds MCl_5, to elucidate the influence of relativistic effects on their properties especially in going from the 5d element Ta to the 6d element Ha. The analysis of the radial distribution of the valence electrons of the metals for electronic configurations obtained as a result of the molecular calculations and their overlap with ligands show opposite trends in behavior for ns_1/2, np_l/2, and (n -1 )d_5/2 orbitals for Ta and Ha in the relativistic and nonrelativistic cases. Relativistic contraction and energetic stabilization of the ns_1/2 and np_l/2 wave functions and expansion and destabilization of the (n-1)d_5/2 orbitals make hahnium pentahalide more covalent than tantalum pentahalide and increase the bond strength. The nonrelativistic treatment of the wave functions results in an increase in ionicity of the MCl_5 molecules in going from Nb to Ha making element Ha an analog of V. Different trends for the relativistic and nonrelativistic cases are also found for ionization potentials, electronic affinities, and energies of charge-transfer transitions as well as the stability of the maximum oxidation state.

Short-term effects of human urine fertiliser and wood ash on soil pH and electrical conductivity

The fertiliser value of human urine has been examined on several crops, yet little is known about its effects on key soil properties of agronomic significance. This study investigated temporal soil salinization potential of human urine fertiliser (HUF). It further looked at combined effects of human urine and wood ash (WA) on soil pH, urine-NH_3 volatilisation, soil electrical conductivity (EC), and basic cation contents of two Acrisols (Adenta and Toje series) from the coastal savannah zone of Ghana. The experiment was a factorial design conducted in the laboratory for 12 weeks. The results indicated an increase in soil pH by 1.2 units for Adenta series and 1 unit for Toje series after one week of HUF application followed by a decline by about 2 pH units for both soil types after twelve weeks. This was attributed to nitrification of ammonium to nitrate leading to acidification. The EC otherwise increased with HUF application creating slightly saline conditions in Toje series and non-saline conditions in Adenta series. When WA was applied with HUF, both soil pH and EC increased. In contrast, the HUF alone slightly salinized Toje series, but both soils remained non-saline whenWA and HUF were applied together. The application ofWA resulted in two-fold increase in Ca, Mg, K, and Na content compared to HUF alone. Hence, WA is a promising amendment of acid soils and could reduce the effect of soluble salts in human urine fertilizer, which is likely to cause soil salinity.