Zugl.: Bamberg, Univ., Magisterarbeit, 1994

Inauguraldiss.--Bonn, 1995. / Bibliogr. p. 118-126.

Diss.--Bonn, 1999. / Bibliogr. p. 397-408. Index.

The present study was focused to develop an analytical method to analyse â-lactam antibiotics present in aqueous solutions and able to be applied directly in the fields. The method here presented is based on the chemical reaction between â-lactam antibiotics with phosphomolybdic acid, a heteropolyacid able to be reduced by the thiols obtained after the acid hydrolysis of the â-lactam antibiotics. The blue product obtained, which is proportional to the antibiotic amount, is adsorbed on polyurethane foam, and the intensity of color is directly evaluated on the solid material by means of diffuse reflectance spectroscopy. For all six evaluated â-lactam antibiotics (amoxicillin, ampicillin, penicillin V, penicillin G, cefotaxime, cefuroxime), the analytical parameters achieved were: LOD = 0.03 µg/ml, LOQ = 0.1 µg/ml, RSD = 4.0 %. The study of possible interferences showed that using solid phase extraction is possible to eliminate even strong interferences as ascorbic acid, cysteine and reducing salts like stannous chloride. The present method has avoided, as much as possible, the use of expensive and contaminating solvents and chemical reagents. The method presents the possibility to be applied using only a desktop scanner and a personal PC for measuring the color of the adsorbed material on the PUF.

A new detector for gas chromatography based on a microwave induced plasma has been developed. In order to record chromatograms emission spectra of diatomics are detected. Also a new method to obtain qualitative information on the analysed organic compound has been developed. The new detection method allows to get information about the atomic composition. In some cases the detector signals can be correlated with the constitution of the analysed substance. The detection method is based on the simultaneous detection of the spectral density of molecular bands of different diatomics as CC, CH, CN, NH, OH and an atomic hydrogen line. The resulting peak areas and the offset of the OH band are correlated with the analysed compounds by multivariate linear regression.

The thesis treats the topic of the characterization and optimization of CMOS compatible photo sensor elements (CPSE). To understand the functionality of a CPSE a pro founded basic knowledge is necessary in the fields of the ray-, wave and quantum optics. Therefore all in this context necessary and principal equations are presented at the beginning of this work. In addition belongs in particular the statistic investigation of the absorption and emission processes in the field of the quantum optics, since these processes are the basis to understand the elementary noise sources within a CPSE. After an introduction to the available technological realization each element of the equivalent circuit diagram is analyzed. The optical quantum efficiency is developed intended for arbitrary angles and optical multi-layer sequences. The internal quantum efficiency is determined with a new mathematical approach and offers thereby more possibilities of the interpretation of the results compared to the classical physical approach which usually proceed from approximation solutions. The physical operation limit of a sensor and thus its efficiency is specified by the power of the noise sources. In this work it is analytically proven that the statements of Einstein concerning the kTC noise of an individual RC combination also apply to coupled RC combinations. Thus a highly simplified viewpoint of the CPSE and the Switched Capacitor amplifier is possible. Several optimization strategies to improve the optical quantum efficiency, for example the oxide perforation, are introduced and realized. The electro optical parameters can be usually determined by the measurement of special test-structures. Furthermore in this work new test-structures are developed, manufactured and measured under the aspect of high insensitivity to measurement errors. These results lead to the development of an Isochor diagram which permits all important design parameters. The Isochor diagram contributes thereby considerably to the conceptual design of a high-dynamic camera including image sensor. In particular the demanded application in the automotive field can be considered in detail. The achievement of the required goal parameters is documented by the measurement of the image sensor in the camera.

A problem in todays Internet infrastructure may occur when a streaming multimedia application is to take place. The information content of video and audio signals that contain moving or changing scenes may simply be too great for Internet clients with low bandwidth capacity if no adaptation is performed. In order to satisfactorily reach clients with various bandwidth capacities some works such as receiver-driven multicast and resilient overlay networks (RON) have been developed. However these efforts mainly call for modification on router level management or place additional layer to the Internet structure, which is not recommended in the nearest future due to the highly acceptance level and widely utilization of the current Internet structure, and the lengthy and tiring standardization process for a new structure or modification to be accepted. We have developed an improved active network approach for distributed and dynamic streaming multimedia environment with heterogeneous bandwidth, such as the case of the Internet. Friendly active network system (FANS) is a sample of our approach. Adopting application level active network (ALAN) mechanism, FANS participants and available media are referred through its universal resource locator (url). The system intercepts traffic flowing from source to destination and performs media post-processing at an intermediate peer. The process is performed at the application level instead of at the router level, which was the original approach of active networks. FANS requires no changes in router level management and puts no additional requirement to the current Internet architecture and, hence, instantly applicable. In comparison with ALAN, FANS possesses two significant differences. From the system overview, ALAN requires three minimum elements: clients, servers, and dynamic proxy servers. FANS, on the other hand, unifies the functionalities of those three elements. Each of peers in FANS is a client, an intermediate peer, and a media server as well. Secondly, FANS members tracking system dynamically detects the existence of a newly joined computers or mobile device, given its url is available and announced. In ALAN, the servers and the middle nodes are priori known and, hence, static. The application level approach and better performance characteristics distinguished also our work with another similar work in this field, which uses router level approach. The approach offers, in general, the following improvements: FANS promotes QoS fairness, in which clients with lower bandwidth are accommodated and receive better quality of service FANS introduces a new algorithm to determine whether or not the involvement of intermediate peer(s) to perform media post-processing enhancement services is necessary. This mechanism is important and advantageous due to the fact that intermediate post-processing increases the delay and, therefore, should only be employed selectively. FANS considers the size of media data and the capacity of clients bandwidth as network parameters that determine the level of quality of service offered. By employing the above techniques, our experiments with the Internet emulator show that our approach improves the reliability of streaming media applications in such environment.

The photocycloadditions of 2-(dialkylamino)propenenitriles to 1-acetylnaphthalene in d6 benzene as solvent proceed with high directional selectivity by fast and photoreversible formation of [2+2]-cycloadducts (tetrahydrocyclobuta[a]naphthalenes) followed by a slower and photoirreversible formation of [4+2]-cycloadducts (1,4-dihydro-1,4-ethanonaphthalenes). With increasing duration of irradiation the product pattern is shifted towards a mixture of diastereomeric [4+2]-adducts in which the isomer with endo-orientation of the dialkylamino group in the ethano bridge is predominating. The endo-[4+2]-adduct of 2-(dipropylamino)-propenenitrile to 1-acetylnaphthalene was isolated in pure form, and its configuration was unambiguously corroborated by a single crystal X-ray structure analysis. Upon thermal activation it is converted in a small fraction via an intermediate biradical to the thermodyna-mically more stable exo-epimer before it is decomposed to the educts. Methyl 1-naphthoate reacts in the same way as 1-acetylnaphthalene but less efficiently.

The use of ICP-OES to determinate Rare Earth Elements in different matrices often fails because of high spectral interferences. To achieve an correct result the use of a sample preparation is advisable. In this work Extractionchromatography is used as sample preparartion. Three different substances were used as stationary phase. These are Triazaheptan-1,4,7,7-tetraaceticacid (DETATA), Tetraphenylmethylendiphosphineoxide. (TPMDPO) und Tri-n-octylphosphineoxide (TOPO). If DETATA is used as staionaric phase the recovery of REE in the final solution is reduced to 40-60% when bivalent ions such as Ni2+ and Fe2+ are present in the sample. So this substance is not reliable in the use as stationaric phase if the sample is a steelmatrix. In highly concentrated KCl-solution as matrix the recovery of REEs increases to 98%. In the second part the results of the experiments with TPMDPO are presented. In the presence of Cr3+, Ni2+ oder Mn2+ the recovery decrease significantly. So this substance is also unusable if the matrix is steel. The third examined organic substance is TOPO. If NH4NO3 is added as salting-out material and after reducing the solution with hydrazine the recovery of REEs is qunatitative. The improvement of the detection limit exceeds the factor of 10 if ICP-OES is the used analysing method.

The active site of the NiFe-hydrogenase from <i>Desulfovibrio vulgaris</i> Miyazaki F was investigated by means of X-ray Absorption Spectroscopy (XAS). Using the Extended X-ray Absorption Fine Structure (EXAFS) the active site was structurally characterized to determine differences between four different catalytic states of the enzyme. The nature of an additional ligand which is present in the oxidized forms of the enzyme was revealed and the distance between both metal atoms of the heterobinuclear site was calculated. Suitable data analyzation techniques were developed using simulated spectra. For the verification of these techniques, spectra from model compounds structurally characterized by other methods were used. To ensure sufficient quality of the spectra a newly developed quality control system using statistical criteria was employed.