Destructive and non-destructive measurements of residual crop residue and phosphorus effects on growth and composition of herbaceous fallow species in the Sahel

Little is known about the residual effects of crop residue (CR) and phosphorus (P) application on the fallow vegetation following repeated cultivation of pearl millet [Pennisetum glaucum (L.) R. Br.] in the Sahel. The objective of this study, therefore, was (i) to measure residual effects of CR, mulched at annual rates of 0, 500, 1000 and 2000 kg CR ha^-1, broadcast P at 0 and 13 kg P ha^-1 and P placement at 0, 1, 3, 5 and 7 kg P ha^-1 on the herbaceous dry matter (HDM) 2 years after the end of the experiment and (ii) to test a remote sensing method for the quantitative estimation of HDM. Compared with unmulched plots, a doubling of HDM was measured in plots that had received at least 500 kg CR ha^-1. Previous broadcast P application led to HDM increases of 14% compared with unfertilised control plots, whereas no residual effects of P placement were detected. Crop residue and P treatments caused significant shifts in flora composition. Digital analysis of colour photographs taken of the fallow vegetation and the bare soil revealed that the number of normalised green band pixels averaged per plot was highly correlated with HDM (r=0.86) and that red band pixels were related to differences in soil surface crusting. Given the traditional use of fallow vegetation as fodder, the results strongly suggest that for the integrated farming systems of the West African Sahel, residual effects of soil amendments on the fallow vegetation should be included in any comprehensive analysis of treatment effects on the agro-pastoral system.

Field measurements of the CO2 evolution rate under different crops during an irrigation cycle in a mountain oasis of Oman

For millennia oasis agriculture has been the backbone of rural livelihood in the desertic Sultanate of Oman. However, little is known about the functioning of these oasis systems, in particular with respect to the C turnover. The objective was to determine the effects of crop, i.e. alfalfa, wheat and bare fallow on the CO2 evolution rate during an irrigation cycle in relation to changes in soil water content and soil temperature. The gravimetric soil water content decreased from initially 24% to approximately 16% within 7 days after irrigation. The mean CO2 evolution rates increased significantly in the order fallow (27.4 mg C m^−2 h^−1) < wheat (45.5 mg C m^−2 h^−1) < alfalfa (97.5 mg C m^−2 h^−1). It can be calculated from these data that the CO2 evolution rate of the alfalfa root system was nearly four times higher than the corresponding rate in the wheat root system. The decline in CO2 evolution rate, especially during the first 4 days after irrigation, was significantly related to the decline in the gravimetric water content, with r = 0.70. CO2 evolution rate and soil temperature at 5 cm depth were negatively correlated (r = -0.56,n = 261) due to increasing soil temperature with decreasing gravimetric water content.

Synthese und Charakterisierung neuartiger, ambipolarer organischer Halbleiter, basierend auf Perylencarboximid-Systemen kombiniert mit funktionalisierten Spirobifluoreneinheiten

Das Ziel der vorliegenden Arbeit war die Synthese und Charakterisierung von donor-funktionalisierten Spiro-Perylencarboximiden, welche für den Einsatz in optoelektronischen Bauelementen wie z.B. organischen Phototransistoren, Feldeffekttransistoren oder Solarzellen vorgesehen sind. Die donorfunktionalisierten Spiro-Perylencarboximide stellen kovalent gebundene Donor-Akzeptor-Verbindungen dar, die unter geeigneter Belichtung einen ladungsgetrennten Zustand bilden können. Die Verbindungen wurden aus unterschiedlichen Spiroamin- und Perylenanhydrid-Edukten synthetisiert, die im Baukastenprinzip zu den entsprechenden Zielverbindungen umgesetzt wurden. Mittels unterschiedlicher Charakterisierungsmethoden (z.B. DSC, TGA, CV, Absorptions- und Fluoreszenzmessungen) wurden die Eigenschaften der neuartigen Zielverbindungen untersucht. Im Rahmen der Arbeit wurden vier neue Spiroamin-Edukte erstmalig synthetisiert und charakterisiert. Sie wurden durch Reduktion aus den bisher noch nicht beschriebenen Nitroverbindungen bzw. mittels Pd-katalysierter Kreuzkupplung (Hartwig-Buchwald-Reaktion) aus einer halogenierten Spiroverbindung erhalten. Als Perylenanhydrid-Edukt wurde erstmals eine perfluorierte Perylenanhydrid-Imid-Verbindung hergestellt. Aus den Spiroamin- und Perylenanhydrid-Edukten wurden insgesamt neun neue, donorfunktionalisierte Spiro-Perylencarboximide synthetisiert. Zusätzlich wurden sechs neuartige Spiro-Perylencarboximide ohne Diphenylamin-Donor hergestellt, die als Vergleichsverbindungen dienten. Die donorfunktionalisierten Spiro-Perylencarboximide besitzen eine Absorption im UV- und sichtbaren Spektralbereich, wobei hohe Extinktionskoeffizienten erreicht werden. Die Verbindungen zeigen in verdünnter Lösung (sowohl in polaren als auch in unpolaren Lösungsmitteln) eine Fluoreszenzquantenausbeute unter 1 %, was auf einen effizienten Ladungstransfer zurückzuführen ist. Alle donorfunktionalisierten Spiro-Perylencarboximide zeigen in den CV-Messungen reversibles Verhalten. Mittels CV-Messungen und optischer Methode konnten die HOMO- und LUMO-Lagen der jeweiligen Molekülhälften berechnet und das Fluoreszenzverhalten der Verbindungen erklärt werden. Ebenso konnten die Auswirkungen von unterschiedlichen Substituenten auf die jeweiligen HOMO-/LUMO-Lagen näher untersucht werden. Die durchgeführten DSC- und TGA-Untersuchungen zeigen hohe morphologische und thermische Stabilität der Verbindungen, wobei Glasübergangstemperaturen > 211 °C, Schmelztemperaturen > 388 °C und Zersetzungstemperaturen > 453 °C gemessen wurden. Diese Werte sind höher als die bisher in der Literatur für ähnliche spiroverknüpfte Verbindungen berichteten. Als besonders interessant haben sich die unsymmetrischen donorfunktionalisierten Spiro-Perylencarboximide herausgestellt. Sie zeigen hohe Löslichkeit in gängigen Lösungsmitteln, sind bis zu einer Molmasse < 1227 g/mol aufdampfbar und bilden stabile, amorphe Schichten.

Photoschaltbare Azobenzol-modifizierte selbstorganisierte Monoschichten auf Gold(111)-Oberflächen

Für die Entwicklung photoschaltbarer selbstorganisierter Monoschichten (SAMs) auf Gold(111)-Oberflächen wurden neue Azobenzol-terminierte Asparagussäure - und Liponsäurederivate synthetisiert. Um den Einfluss lateraler Wasserstoffbrückenbindungen auf Qualität und Orientierungsordnung der Schichten zu untersuchen, wurden Monolagen, die durch amid- und esterverknüpfte Verbindungen gebildet wurden, miteinander verglichen. Die Filmbildung aus der Lösung wurde in situ durch optische Frequenzverdopplung (SHG) untersucht und die Photoreaktivität mittels Kontaktwinkelmessungen, Oberflächen-Plasmonenresonanz (SPR) und Ellipsometrie verfolgt. SAMs auf Gold wurden außerdem mit Hilfe von Röntgenphotoelektronenspektroskopie (XPS), Nahkanten-Reflexions-Röntgenabsorptionsspektroskopie (NEXAFS) und Infrarot-Reflexionsabsorptionsspektroskopie (IRRAS) charakterisiert, um die Filmqualität, die Bindung ans Substrat und Orientierungsordnung im Film zu ermitteln. Da die Chemisorption auf polykristallinem Gold formal der Koordinationschemie von 1,2-Dithiolan-Derivaten gegenüber nullwertigen Edelmetall-Zentralatomen entspricht, wurden etliche Pt-Komplexe durch oxidative Addition an [Pt(PPh3)4] dargestellt. Im Zusammenhang mit der Darstellung der Asparagussäure wurde die Kristallstruktur von [pipH]2[WS4] und der neuen Verbindungen [pipH]3[WS4](HS) und [pipH]4[WS4][WOS3] (pip = Piperidin) bestimmt. Wasserstoffbrückenbindungen zwischen den Piperidinium-Kationen und den Thiowolframat-Anionen spielen eine dominante strukturelle Rolle.

Theory for the Photoacoustic Response to X-Ray Absorption

A microscopic theory is presented for the photoacoustic effect induced in solids by x-ray absorption. The photoacoustic effect results from the thermalization of the excited Auger electrons and photoelectrons. We explain the dependence of the photoacoustic signal S on photon energy and the proportionality to the x-ray absorption coefficient in agreement with recent experiments on Cu. Results are presented for the dependence of S on photon energy, sample thickness, and the electronic structure of the absorbing solid.

Theory for Optical Absorption in Small Clusters: Dependence on Atomic Structure and Cluster Size

We present a theory which permits for the first time a detailed analysis of the dependence of the absorption spectrum on atomic structure and cluster size. Thus, we determine the development of the collective excitations in small clusters and show that their broadening depends sensitively on the tomic structure, in particular at the surface. Results for Hg_n^+ clusters show that the plasmon energy is close to its jellium value in the case of spherical-like structures, but is in general between w_p/ \wurzel{3} and w_p/ \wurzel{2} for compact clusters. A particular success of our theory is the identification of the excitations contributing to the absorption peaks.

Photoionization of Kr 4s: III. Detailed and extended measurements of the Kr 4s-electron ionization cross section

Absolute Kr 4s-electron photoionization cross sections as a function of the exciting-photon energy were measured by photon-induced fluorescence spectroscopy (PIFS) at improved primary-energy resolution. The cross sections were determined from threshold to 33.5 eV and to 90 eV with primary-photon bandwidths of 25 meV and 50 meV, respectively. The measurements were compared with experimental data and selected theoretical calculations for the direct Kr 4s-electron photoionization cross sections.

Molecular effects on the cross section for pair production and their importance in the evaluation of the total photonuclear cross section of {^16}O in the {\delta-resonance} region

The screening correction to the coherent pair-production cross section on the oxygen molecule has been calculated using self-consistent relativistic wave functions for the one-center and two-center Coulomb potentials. It is shown that the modification of the wave function due to molecular binding and the interference between contributions from the two atoms have both sizeable effects on the screening correction. The so-obtained coherent pair-production cross section which makes up the largest part of the total atomic cross section was used to evaluate the total nuclear absorption cross section from photon attenuation measurements on liquid oxygen. The result agrees with cross sections for other nuclei if A-scaling is assumed. The molecular effect on the pair cross section amounts to 15 % of the nuclear cross section in the {\delta-resonance} region.

Hyperspectral field measurements to determine dry matter yield and nutritive value of legume-grass swards

Summary: Productivity, botanical composition and forage quality of legume-grass swards are important factors for successful arable farming in both organic and conventional farming systems. As these attributes can vary considerably within a field, a non-destructive method of detection while doing other tasks would facilitate a more targeted management of crops, forage and nutrients in the soil-plant-animal system. This study was undertaken to explore the potential of field spectral measurements for a non destructive prediction of dry matter (DM) yield, legume proportion in the sward, metabolizable energy (ME), ash content, crude protein (CP) and acid detergent fiber (ADF) of legume-grass mixtures. Two experiments were conducted in a greenhouse under controlled conditions which allowed collecting spectral measurements which were free from interferences such as wind, passing clouds and changing angles of solar irradiation. In a second step this initial investigation was evaluated in the field by a two year experiment with the same legume-grass swards. Several techniques for analysis of the hyperspectral data set were examined in this study: four vegetation indices (VIs): simple ratio (SR), normalized difference vegetation index (NDVI), enhanced vegetation index (EVI) and red edge position (REP), two-waveband reflectance ratios, modified partial least squares (MPLS) regression and stepwise multiple linear regression (SMLR). The results showed the potential of field spectroscopy and proved its usefulness for the prediction of DM yield, ash content and CP across a wide range of legume proportion and growth stage. In all investigations prediction accuracy of DM yield, ash content and CP could be improved by legume-specific calibrations which included mixtures and pure swards of perennial ryegrass and of the respective legume species. The comparison between the greenhouse and the field experiments showed that the interaction between spectral reflectance and weather conditions as well as incidence angle of light interfered with an accurate determination of DM yield. Further research is hence needed to improve the validity of spectral measurements in the field. Furthermore, the developed models should be tested on varying sites and vegetation periods to enhance the robustness and portability of the models to other environmental conditions.

Synthesis and Characterization of Novel Spiro-Starburst-Structures as Blue Light Emitters and Zeolites

Spiro-starburst-structures with symmetric globular structures in forms of first and second generations that readily form stable amorphous glasses have been synthesized and then characterised in this work. During the synthesis of these materials, possibilities of the extension of the chains of the phenyl rings in 2,2’,7 and 7’-positions of the central core of the spirobifluorene as well as the 2’,7 and 7’-positions of the terminal spirobifluorene units of the spiro-starburst-structures have been investigated so that solubilities and morphologies of the compounds are not negatively influenced. Their morphological properties have been explored by recording their decomposition temperature and glass transition temperature. These compounds possessing two perpendicular arrangement of the two molecular halves show high glass transition temperature (Tg), which is one of the most important parameter indicating the stability of the amorphous state of the material for optoelectronic devices like organic light emitting diodes. Within the species of second generation compounds, for example, 4-spiro3 shows the highest Tg (330 °C) and the highest branching degree. When one [4B(SBF)SBF-SBF 84] or two [4SBFSBF-SBF 79] terminal spirobifluorene units are removed, the Tg decreases to 318 °C and 307 °C respectively. Photo absorption and fluorescence spectra and cyclic voltammetry measurements are taken in account to characterize the optoelectronic properties of the compounds. Spiro-starburst-structures emit radiation in the blue region of the visible spectrum. The peak maxima of absorption and emission spectra are observed to be at higher wavelength in the molecules with longer chromophore chains than in the molecules with shorter chromophore chains. Excitation spectra are monitored with their emission peak maxima. The increasing absorbing species in molecule leads to increasing molar extinction coefficient. In the case of 4B(TP)SBF-SBF 53 and 4B(SBF)SBF-SBF 84, the greater values of the molar extinction coefficients (43*104 and 44*104 L mol-1 cm-1 respectively) are the evidences of the presence of four times octiphenyl conjugation rings and eight times terminal fluorene units respectively. The optical properties of solid states of these compounds in the form of thin film indicate that the intermolecular interaction and aggregation of individual molecules in neat amorphous films are effectively hindered by their sterically demanding structures. Accordingly, in solid state, they behave like isolated molecules in highly dilute solution. Cyclic voltammetry measurements of these compounds show electrochemically reversibility and stability. Furthermore, the zeolitic nature (host-guest) of the molecular sieve of the synthesized spiro-starburst-structures has been analysed by thermogravimetric analysis method.

Patent DE10 2004 037 519 B4 “Sensor Process and Device for Determining a Physical Value“. A Proof of Concept

At present, a fraction of 0.1 - 0.2% of the patients undergoing surgery become aware during the process. The situation is referred to as anesthesia awareness and is obviously very traumatic for the person experiencing it. The reason for its occurrence is mostly an insufficient dosage of the narcotic Propofol combined with the incapability of the technology monitoring the depth of the patient’s anesthetic state to notice the patient becoming aware. A solution can be a highly sensitive and selective real time monitoring device for Propofol based on optical absorption spectroscopy. Its working principle has been postulated by Prof. Dr. habil. H. Hillmer and formulated in DE10 2004 037 519 B4, filed on Aug 30th, 2004. It consists of the exploitation of Intra Cavity Absorption effects in a two mode laser system. In this Dissertation, a two mode external cavity semiconductor laser, which has been developed previously to this work is enhanced and optimized to a functional sensor. Enhancements include the implementation of variable couplers into the system and the implementation of a collimator arrangement into which samples can be introduced. A sample holder and cells are developed and characterized with a focus on compatibility with the measurement approach. Further optimization concerns the overall performance of the system: scattering sources are reduced by re-splicing all fiber-to-fiber connections, parasitic cavities are eliminated by suppressing the Fresnel reflexes of all one fiber ends by means of optical isolators and wavelength stability of the system is improved by the implementation of thermal insulation to the Fiber Bragg Gratings (FBG). The final laser sensor is characterized in detail thermally and optically. Two separate modes are obtained at 1542.0 and 1542.5 nm, tunable in a range of 1nm each. Mode Full Width at Half Maximum (FWHM) is 0.06nm and Signal to Noise Ratio (SNR) is as high as 55 dB. Independent of tuning the two modes of the system can always be equalized in intensity, which is important as the delicacy of the intensity equilibrium is one of the main sensitivity enhancing effects formulated in DE10 2004 037 519 B4. For the proof of concept (POC) measurements the target substance Propofol is diluted in the solvents Acetone and DiChloroMethane (DCM), which have been investigated for compatibility with Propofol beforehand. Eight measurement series (two solvents, two cell lengths and two different mode spacings) are taken, which draw a uniform picture: mode intensity ratio responds linearly to an increase of Propofol in all cases. The slope of the linear response indicates the sensitivity of the system. The eight series are split up into two groups: measurements taken in long cells and measurements taken in short cells.

Highly Sensitive Sensor Based On Intracavity Laser Absorption Spectroscopy By Means of Relative Intensity Noise

This thesis concerns with the main aspects of medical trace molecules detection by means of intracavity laser absorption spectroscopy (ICLAS), namely with the equirements for highly sensitive, highly selective, low price, and compact size sensor. A novel two modes semiconductor laser sensor is demonstrated. Its operation principle is based on the competition between these two modes. The sensor sensitivity is improved when the sample is placed inside the two modes laser cavity, and the competition between the two modes exists. The effects of the mode competition in ICLAS are discussed theoretically and experimentally. The sensor selectivity is enhanced using external cavity diode laser (ECDL) configuration, where the tuning range only depends on the external cavity configuration. In order to considerably reduce the sensor cost, relative intensity noise (RIN) is chosen for monitoring the intensity ratio of the two modes. RIN is found to be an excellent indicator for the two modes intensity ratio variations which strongly supports the sensor methodology. On the other hand, it has been found that, wavelength tuning has no effect on the RIN spectrum which is very beneficial for the proposed detection principle. In order to use the sensor for medical applications, the absorption line of an anesthetic sample, propofol, is measured. Propofol has been dissolved in various solvents. RIN has been chosen to monitor the sensor response. From the measured spectra, the sensor sensitivity enhancement factor is found to be of the order of 10^(3) times of the conventional laser spectroscopy.

Synthesis and characterisation of novel nitrogen and fluorine containing spirobifluorene derivatives for electronic applications and crystal engineering

Among organic materials, spirobifluorene derivatives represent a very attractive class of materials for electronic devices. These compounds have high melting points, glass transitions temperatures and morphological stability, which makes these materials suitable for organic electronic applications. In addition, some of spirobifluorenes can form porous supramolecular associations with significant volumes available for the inclusion of guests. These molecular associations based on the spirobifluorenes are noteworthy because they are purely molecular analogues of zeolites and other microporous solids, with potential applications in separation, catalysis, sensing and other areas.

Sensorische Erfassung von Grünlandbiomassen als Grundlage für ein teilflächenspezifisches Management im Ökologischen Landbau

Vor dem Hintergund der Integration des wissensbasierten Managementsystems Precision Farming in den Ökologischen Landbau wurde die Umsetzung bestehender sowie neu zu entwickelnder Strategien evaluiert und diskutiert. Mit Blick auf eine im Precision Farming maßgebende kosteneffiziente Ertragserfassung der im Ökologischen Landbau flächenrelevanten Leguminosen-Grasgemenge wurden in zwei weiteren Beiträgen die Schätzgüten von Ultraschall- und Spektralsensorik in singulärer und kombinierter Anwendung analysiert. Das Ziel des Precision Farming, ein angepasstes Management bezogen auf die flächeninterne Variabilität der Standorte umzusetzen, und damit einer Reduzierung von Betriebsmitteln, Energie, Arbeit und Umwelteffekten bei gleichzeitiger Effektivitätssteigerung und einer ökonomischen Optimierung zu erreichen, deckt sich mit wesentlichen Bestrebungen im Ökogischen Landbau. Es sind vorrangig Maßnahmen zur Erfassung der Variabilität von Standortfaktoren wie Geländerelief, Bodenbeprobung und scheinbare elektrische Leitfähigkeit sowie der Ertragserfassung über Mähdrescher, die direkt im Ökologischen Landbau Anwendung finden können. Dagegen sind dynamisch angepasste Applikationen zur Düngung, im Pflanzenschutz und zur Beseitigung von Unkräutern aufgrund komplexer Interaktionen und eines eher passiven Charakters dieser Maßnahmen im Ökologischen Landbau nur bei Veränderung der Applikationsmodelle und unter Einbindung weiterer dynamischer Daten umsetzbar. Beispiele hiefür sind einzubeziehende Mineralisierungsprozesse im Boden und organischem Dünger bei der Düngemengenberechnung, schwer ortsspezifisch zuzuordnende präventive Maßnamen im Pflanzenschutz sowie Einflüsse auf bodenmikrobiologische Prozesse bei Hack- oder Striegelgängen. Die indirekten Regulationsmechanismen des Ökologischen Landbaus begrenzen daher die bisher eher auf eine direkte Wirkung ausgelegten dynamisch angepassten Applikationen des konventionellen Precision Farming. Ergänzend sind innovative neue Strategien denkbar, von denen die qualitätsbezogene Ernte, der Einsatz hochsensibler Sensoren zur Früherkennung von Pflanzenkrankheiten oder die gezielte teilflächen- und naturschutzorientierte Bewirtschaftung exemplarisch in der Arbeit vorgestellt werden. Für die häufig große Flächenanteile umfassenden Leguminosen-Grasgemenge wurden für eine kostengünstige und flexibel einsetzbare Ertragserfassung die Ultraschalldistanzmessung zur Charakterisierung der Bestandeshöhe sowie verschiedene spektrale Vegetationsindices als Schätzindikatoren analysiert. Die Vegetationsindices wurden aus hyperspektralen Daten nach publizierten Gleichungen errechnet sowie als „Normalized Difference Spectral Index“ (NDSI) stufenweise aus allen möglichen Wellenlängenkombinationen ermittelt. Die Analyse erfolgte für Ultraschall und Vegetationsindices in alleiniger und in kombinierter Anwendung, um mögliche kompensatorische Effekte zu nutzen. In alleiniger Anwendung erreichte die Ultraschallbestandeshöhe durchweg bessere Schätzgüten, als alle einzelnen Vegetationsindices. Bei den letztgenannten erreichten insbesondere auf Wasserabsorptionsbanden basierende Vegetationsindices eine höhere Schätzgenauigkeit als traditionelle Rot/Infrarot-Indices. Die Kombination beider Sensorda-ten ließ eine weitere Steigerung der Schätzgüte erkennen, insbesondere bei bestandesspezifischer Kalibration. Hierbei kompensieren die Vegetationsindices Fehlschätzungen der Höhenmessung bei diskontinuierlichen Bestandesdichtenänderungen entlang des Höhengradienten, wie sie beim Ährenschieben oder durch einzelne hochwachsende Arten verursacht werden. Die Kombination der Ultraschallbestandeshöhe mit Vegetationsindices weist das Potential zur Entwicklung kostengünstiger Ertragssensoren für Leguminosen-Grasgemenge auf. Weitere Untersuchungen mit hyperspektralen Vegetationsindices anderer Berechnungstrukturen sowie die Einbindung von mehr als zwei Wellenlängen sind hinsichtlich der Entwicklung höherer Schätzgüten notwendig. Ebenso gilt es, Kalibrierungen und Validationen der Sensorkombination im artenreichen Grasland durchzuführen. Die Ertragserfassung in den Leguminosen-Grasgemengen stellt einen wichtigen Beitrag zur Erstellung einer Ertragshistorie in den vielfältigen Fruchtfolgen des Ökologischen Landbaus dar und ermöglicht eine verbesserte Einschätzung von Produktionspotenzialen und Defizitarealen für ein standortangepasstes Management.