Transition Metal Complexes of Schiff Bases with Azide and Thiocyanate as Coligands:Spectral and Structural Investigations

Metallo-organic chemistry,incorporating the frontiers of both inorganic and organic chemical aspects,is a topic of utility concern.The first exploration of coordinated metal complexes dates back to the ninettenth century,during the days of Alfred Werner.Thereafter,inorganic chemistry witnessed a great outflow of coordination compounds,with unique structural characteristics and diverse applicatons.The diversity in structures exhibited by the coordination complexes of multidentate ligands have led to their usage as sensors,models for enzyme mimetic centers,medicines etc.The liganda chosen are of prime importance in determining the properties of coordination compounds.Schiff bases are compounds obtained by the condensation of an aidehyde or ketone with an amine.The chemical properties of Schiff bases and their complexes are widely explored in recent years owing to their pharmacological activity,their catalytic activities and so on.On the other hand pseudohalides like azide and thiocyanate are versatile candidates for the construction of dimeric or polymeric complexes having excellent properties and diverse applications.So a combination of the Schiff bases and the pseudohalogens for the synthesis of metal complexes can bring about interesting results.An attempt into this area is the besis of this Ph.D theis.

Studies on Catalysis by Ordered Mesoporous SBA-15 Materials Modified with Transition Metals

To meet the challenges related to the chemical industry,development of efficient catalysts is necessary.The mesoporous materials like SBA-15 are considered as good catalyst candidates of 21st century.SBA-15 mesoporous materials are catalytically inactive,but allow the dispersion of catalytically active phases into the framework.So these materials can be considered as an interesting alternative for preparing catalytically active metal nanoparticles in-situ into it.In the present work various transition metals are incorporated to improve the catalytic activity of SBA-15 material.The fundamental aspects of the preparation,characterization and the activity studies are briefly viewed in this thesis. Systematic investigation of the physico-chemical properties and catalytic activity studies of the prepared materials were carried out and presented in this Study.

Fish habitats and species assemblage in the selected rivers of Kerala and investigation on life history traits of Puntius carnaticus(Jerdon,1849)

This thesis entitled Fish habitats and species assemblage in the selected rivers of kerala and investigation on life history traits of puntius carnaticus (JERDON,1849). Ecology is a new and exceedingly complex field of study, even though its concept was recognized by the Apostles in their use of the phrase ‘all flesh is grass.central role to play both in order to understand better the biodiversity phenomenon and to be able to draw up clear guidelines for careful resource management. In a review by WWF, IUCN and UNEP on the ways of conserving genetic diversity of freshwater fish it was recommended that the best way to conserve species diversity is to conserve habitat.The habitat studies in freshwater ecosystems are very essential for the proper understanding and management of human impact on fish diversity, to study the relationship between habitat variables and fish species assemblage structure, quantification of ecosystem degradation, habitat quality and biotic integrity of the ecosystems, development of habitat suitability index (I-ISI) models and classification of river reaches based on their physico-chemical properties. Therefore in the present study an attempt was made to assess the biodiversity potential and the relationship between habitat variables and fish species assemblage structure in six major river systems of Kerala which would be very useful in impressing upon the seriousness of habitat degradIn the present study, in Kabbini river system 15 locations encompassing between 721 946m above MSL were surveyed.ation and biotic devastation undergone in the major river systems of Kerala.During the present study the Habitat Quality Score (HQ) developed by the Ohio EPA was applied for the first time in India.The result of the present study revealed that, among various variables analysed, altitude has a very significant influence in deciding the fish diversity in six major river systems of Kerala. The fish diversity studied on the basis of Shanon-Weiner and Simpson diversity indices revealed that even though some minor variations occur with the suitability and complexity of habitats, the altitude showed inverse relationship with fish diversity.The present study revealed that the National Policy on the interlinking of rivers would permanently alter the HSI indices of the above mentioned fish species, which are now solely protected by the individuality of the rivers where their limited occurrence was notice.

Biochemical and Biotechnological investigations on the water-fern Salvinia molesta Mitchell

The present work is focussed mainly on the utilization of this weed-biomass on a biochemical and biotechnological basis. Before designing scientific and systematic utilization of any given biomass, the detailed analysis of its chemical componets is essential. Hence, as the preliminary part of the experimental works, samples of Salvinia were analysed for its chemical constituents.Before designing scientific and systematic utilization of any given biomass, the detailed analysis of its chemical componets is essential .The composition of the substrate contributes much to the nutritive value of mushrooms. Hence, alterations in the nutritive value of mushrooms (in terms of total carbohydrates, proteins, lipids and minerals) in response to Salvinia as substrate were analyzed.Substrate after mushroom harvest (spent substrate) can be utilized for various purposes such as cattle feed, as a source of degradative enzymes, as a substrate for other mushrooms and as garden manure. But studies are limited with regard to the utilization of Pleurotus spent substrate as garden manure. So the value of spent substrate as an organic supplement and its multidimensional impacts on soil chemical status, soil microbial population dynamics and plant growth (Amhurium andreanum) were carried out.Major findings of this work have got much relevance in designing measures to utilize different types of plant biomass, especially aquatic weeds, with the aid of a powerful biological tool, the lignocellulolytic fungus, Pleurorus

Adsoption-induced restructuring of gold nanochains

The chemical properties of single-atomic chains of gold atoms are investigated using density functional calculations. The nanochains are shown to be unusually chemically active with strong chemisorption of oxygen atoms and carbon monoxide. The chemisorption energies vary significantly with the strain/stress conditions for the chain. Oxygen atoms are found to energetically prefer to get incorporated into a chain forming a new type of gold-oxygen nanochain with a conductance of one quantum unit. We suggest that the long bond lengths observed in electron microscopy investigations of gold chains can be due to oxygen incorporation.

Effect of industrial pollution on the benthic communities of a tropical estuary

Cochin backwaters, a tropical barbuilt estuary is well known for its prawn, molluscan and demersal fisheries. Also it formed the dumping area for sewage,235 retting of husks and discharge of effluents from industries located on either side of it. As a result the fishery is being gradually dwindled year after year due to the lowering of the water quality. The effect of industrial polution on the benthic community of this tropical estuary was worked out. An area extending over 21 km from the mouth of the estuary to upstream of industrial belt was selected. Temporal and spatial variations of 16 environmental parameters at 9 stations along the area were monitored monthly during 1981. Benthic fauna of these 9 stations consisted of amphipods , polychaetes, isopods, tanaidaceans, molluscs and other crustaceans (Decapods, Acetes, Alpheids, Balanus, insect larvae, chironomid larvae, cumacea and some fresh water forms ). Apart from these, sea anemone, flat worms, nematodes, sipunculoids, echinoderms and fishes were also encountered. 75 species belonging to 31 faunal groups were identified. Of these 31 groups, amphipods, polychaedes, isopods, tanaidaceans and molluscs were numerically abundant. Rest of the 26 groups (including 13 riverine forms) were found less significant due to their rare occurrence/low numerical abundance. Polychaetes and molluscs were the only major groups present at all the stations.

‘‘catalysis by nano sulfated titania modified by transition metals"

in the present study, we have prepared and evaluated the physical and chemical properties and catalytic activities of transition metal loaded sulfated titania via the sol-gel route. Sol-gel method is widely used for preparing porous materials having controlled properties and leads to the formation of oxide particles in nano range, which are spherical or interconnected to each other. Characterization using various physico-chemical techniques and a detailed study of acidic properties are also carried out. Some reactions of industrial importance such as Friedel-Crafts reaction, fen-butylation of phenol,Beckmann rearrangement of cyclohexanone oxime, nitration of phenol and photochemical degradation of methylene blue have been selected for catalytic activity study in the present venture. The work is organized into eight chapters

Effect of cycling on the magnetization of ion exchanged magnetic nanocomposite based on polystyrene

Magnetic nanocomposites containing iron oxide particles embedded in a polymer matrix have been synthesized using the method of ion exchange. They have been characterized by using low temperature and room temperature magnetic measurements and Mo¨ ssbauer spectroscopy. The iron content in these samples has also been determined. The results have been analysed and explained. The physical and chemical properties of these nanocomposite materials are different from those of the bulk. Some of the unique properties of these materials find application in information storage, color imaging, ferrofluids and magnetic refrigeration

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Adsorption of element 112 on a Au surface

Während der letzten 20 Jahre hat sich das Periodensystem bis zu den Elementen 114 und 116 erweitert. Diese sind kernphysikalisch nachgewiesen, so dass jetzt die chemische Untersuchung an erster Selle steht. Nachdem sich das Periodensystem bis zum Element 108 so verhält, wie man es dem Periodensystem nach annimmt, wird in dieser Arbeit die Chemie des Elements 112 untersucht. Dabei geht es um die Adsorptionsenergie auf einer Gold-Ober fläche, weil dies der physikalisch/chemische Prozess ist, der bei der Analyse angewandt wird. Die Methode, die in dieser Arbeit angwandt wird, ist die relativistische Dichtefunktionalmethode. Im ersten Teil wird das Vielkörperproblem in allgemeiner Form behandelt, und im zweiten die grundlegenden Eigenschaften und Formulierungen der Dichtefunktionaltheorie. Die Arbeit beschreibt zwei prinzipiell unterschiedliche Ansätze, wie die Adsorptionsenergie berechnet werden kann. Zum einen ist es die sogenannte Clustermethode, bei der ein Atom auf ein relativ kleines Cluster aufgebracht und dessen Adsorptionsenergie berechnet wird. Wenn es gelingt, die Konvergenz mit der Größe des Clusters zu erreichen, sollte dies zu einem Wert für die Adsorptionsenergie führen. Leider zeigt sich in den Rechnungen, dass aufgrund des zeitlichen Aufwandes die Konvergenz für die Clusterrechnungen nicht erreicht wird. Es werden sehr ausführlich die drei verschiedenen Adsorptionsplätze, die Top-, die Brücken- und die Muldenposition, berechnet. Sehr viel mehr Erfolg erzielt man mit der Einbettungsmethode, bei der ein kleiner Cluster von vielen weiteren Atomen an den Positionen, die sie im Festkörpers auf die Adsorptionsenergie soweit sichergestellt ist, dass physikalisch-chemisch gute Ergebnisse erzielt werden. Alle hier gennanten Rechnungen sowohl mit der Cluster- wie mit der Einbettungsmethode verlangen sehr, sehr lange Rechenzeiten, die, wie oben bereits erwähnt, nicht zu einer Konvergenz für die Clusterrechnungen ausreichten. In der Arbeit wird bei allen Rechnungen sehr detailliert auf die Abhängigkeit von den möglichen Basissätzen eingegangen, die ebenfalls in entscheidender Weise zur Länge und Qualität der Rechnungen beitragen. Die auskonvergierten Rechnungen werden in der Form von Potentialkurven, Density of States (DOS), Overlap Populations sowie Partial Crystal Overlap Populations analysiert. Im Ergebnis zeigt sich, dass die Adsoptionsenergie für das Element 112 auf einer Goldoberfläche ca. 0.2 eV niedriger ist als die Adsorption von Quecksilber auf der gleichen Ober fläche. Mit diesem Ergebnis haben die experimentellen Kernchemiker einen Wert an der Hand, mit dem sie eine Anhaltspunkt haben, wo sie bei den Messungen die wenigen zu erwartenden Ereignisse finden können.

Untersuchung der Adsorptionskinetik photoschaltbarer azobenzolfunktionalisierter selbstorganisierter Monolagen mit optischer Frequenzverdopplung

In dieser Arbeit wurde das Adsorptionsverhalten zweier azobenzolfunktionalisierter Liganden auf Goldoberflächen untersucht. Diese Liganden zeichnen sich dadurch aus, dass sie mithilfe von Licht bestimmter Wellenlängen zwischen zwei Isomerisierungszuständen – sowohl in Lösung als auch in den auf der Oberfläche resultierenden Monolage – hin und her geschaltet werden können. Somit ist es möglich, Oberflächen herzustellen, deren physikalische und chemische Eigenschaften zwischen zwei Zuständen variiert werden können. Die Messungen des Adsorptionsverhaltens wurden mittels optischer Frequenzverdopplung durchgeführt. Diese Messmethode ist höchst grenzflächensensitiv und ermöglicht es somit die Adsorption der Liganden in situ und ich Echtzeit zu verfolgen. Neben den Adsorptionsmessungen wurde auch die Phase des frequenzverdoppelten Signals über eine Interferenzmethode gemessen. Die Ergebnisse dieser Phasenmessungen ermöglichen es, eine Aussage über eine mögliche Nichtlinearität der untersuchten Moleküle zu treffen. An die in den Adsorptionsmessungen gewonnenen Messdaten wurden drei kinetische Standardmodelle angepasst. Beschreibt eines dieser Modelle den im Experiment bestimmten Adsorptionsverlauf, kann eine Aussage über die zugrunde liegenden Prozesse des Adsorptionsvorganges getroffen werden. Die Ergebnisse der Adsorptionsmessungen zeigen einen deutlichen Einfluss des Isomerisierungszustandes der Liganden auf den Verlauf der Adsorption. Liegen die Moleküle im geschalteten Zustand vor, so verläuft die Adsorption langsamer. Weiterhin konnte gezeigt werden, dass ebenso intermolekulare Wechselwirkungen über Wasserstoffbrückenbindungen einen verlangsamenden Einfluss auf die Adsorption der Liganden haben. In den durchgeführten Phasenmessungen zeigte sich darüber hinaus, dass Liganden, die über an die Azobenzolgruppe angebundene Amidgruppen verfügen, eine Nichtlinearität aufweisen. Diese Nichtlinearität ist zudem vom Isomerisierungszustand der Liganden abhängig. In den kinetischen Untersuchungen konnte darüber hinaus gezeigt werden, dass sich die Adsorption der Liganden bis auf eine Ausnahme durch die Langmuirkinetik 2. Ordnung beschreiben lässt. Somit handelt es ich bei der Adsorption der untersuchten Liganden um eine Reaktion, der eine Bindungsspaltung voran geht. Dieser Befund konnte durch Vergleich mit weiteren Experimenten bestätigt werden.

Agricultural practices and horizontal nutrient balances in urban gardens and the alternative use of urban agricultural land in Khartoum, Sudan

The surge in the urban population evident in most developing countries is a worldwide phenomenon, and often the result of drought, conflicts, poverty and the lack of education opportunities. In parallel with the growth of the cities is the growing need for food which leads to the burgeoning expansion of urban and peri-urban agriculture (UPA). In this context, urban agriculture (UA) contributes significantly to supplying local markets with both vegetable and animal produce. As an income generating activity, UA also contributes to the livelihoods of poor urban dwellers. In order to evaluate the nutrient status of urban soils in relation to garden management, this study assessed nutrient fluxes (inputs and outputs) in gardens on urban Gerif soils on the banks of the River Nile in Khartoum, the capital city of Sudan. To achieve this objective, a preliminary baseline survey was carried out to describe the structure of the existing garden systems. In cooperation with the author of another PhD thesis (Ms. Ishtiag Abdalla), alternative uses of cow dung in brick making kilns in urban Khartoum were assessed; and the socio-economic criteria of the brick kiln owners or agents, economical and plant nutritional value of animal dung and the gaseous emission related to brick making activities were assessed. A total of 40 household heads were interviewed using a semi-structured questionnaire to collect information on demographic, socio-economic and migratory characteristics of the household members, the gardening systems used and the problems encountered in urban gardening. Based on the results of this survey, gardens were divided into three groups: mixed vegetable-fodder gardens, mixed vegetable-subsistence livestock gardens and pure vegetable gardens. The results revealed that UA is the exclusive domain of men, 80% of them non-native to Khartoum. The harvested produce in all gardens was market oriented and represented the main source of income for 83% of the gardeners. Fast growing leafy vegetables such as Jew’s mallow (Corchorous olitorius L.), purslane (Portulaca oleracea L.) and rocket (Eruca sativa Mill.) were the dominant cultivated species. Most of the gardens (95%) were continuously cultivated throughout the year without any fallow period, unless they were flooded. Gardeners were not generally aware of the importance of crop diversity, which may help them overcome the strongly fluctuating market prices for their produce and thereby strengthen the contributions of UA to the overall productivity of the city. To measure nutrient fluxes, four gardens were selected and their nutrients inputs and outputs flows were monitored. In each garden, all plots were monitored for quantification of nutrient inputs and outputs. To determine soil chemical fertility parameters in each of the studied gardens, soil samples were taken from three selected plots at the beginning of the study in October 2007 (gardens L1, L2 and H1) and in April 2008 (garden H2) and at the end of the study period in March 2010. Additional soil sampling occurred in May 2009 to assess changes in the soil nutrient status after the River Nile flood of 2008 had receded. Samples of rain and irrigation water (river and well-water) were analyzed for nitrogen (N), phosphorus (P), potassium (K) and carbon (C) content to determine their nutrient inputs. Catchment traps were installed to quantify the sediment yield from the River Nile flood. To quantify the nutrient inputs of sediments, samples were analyzed for N, P, K and organic carbon (Corg) content, cation exchange capacity (CEC) and the particle size distribution. The total nutrient inputs were calculated by multiplying the sediment nutrient content by total sediment deposits on individual gardens. Nutrient output in the form of harvested yield was quantified at harvest of each crop. Plant samples from each field were dried, and analyzed for their N, P, K and Corg content. Cumulative leaching losses of mineral N and P were estimated in a single plot in garden L1 from December 1st 2008 to July 1st 2009 using 12 ion exchange resins cartridges. Nutrients were extracted and analyzed for nitrate (NO3--N), ammonium (NH4+-N) and phosphate PO4-3-P. Changes in soil nutrient balance were assessed as inputs minus outputs. The results showed that across gardens, soil N and P concentrations increased from 2007 to 2009, while particle size distribution remained unchanged. Sediment loads and their respective contents of N, P and Corg decreased significantly (P < 0.05) from the gardens of the downstream lowlands (L1 and L2) to the gardens of the upstream highlands (H1 and H2). No significant difference was found in K deposits. None of the gardens received organic fertilizers and the only mineral fertilizer applied was urea (46-0-0). This equaled 29, 30, 54, and 67% of total N inputs to gardens L1, L2, H1, and H2, respectively. Sediment deposits of the River Nile floods contributed on average 67, 94, 6 and 42% to the total N, P, K and C inputs in lowland gardens and 33, 86, 4 and 37% of total N, P, K and C inputs in highland gardens. Irrigation water and rainfall contributed substantially to K inputs representing 96, 92, 94 and 96% of total K influxes in garden L1, L2, H1 and H2, respectively. Following the same order, total annual DM yields in the gardens were 26, 18, 16 and 1.8 t ha-1. Annual leaching losses were estimated to be 0.02 kg NH4+-N ha-1 (SE = 0.004), 0.03 kg NO3--N ha-1 (SE = 0.002) and 0.005 kg PO4-3-P ha-1 (SE = 0.0007). Differences between nutrient inputs and outputs indicated negative nutrient balances for P and K and positive balances of N and C for all gardens. The negative balances in P and K call for adoptions of new agricultural techniques such as regular manure additions or mulching which may enhance the soil organic matter status. A quantification of fluxes not measured in our study such as N2-fixation, dry deposition and gaseous emissions of C and N would be necessary to comprehensively assess the sustainability of these intensive gardening systems. The second part of the survey dealt with the brick making kilns. A total of 50 brick kiln owners/or agents were interviewed from July to August 2009, using a semi-structured questionnaire. The data collected included general information such as age, family size, education, land ownership, number of kilns managed and/or owned, number of months that kilns were in operation, quantity of inputs (cow dung and fuel wood) used, prices of inputs and products across the production season. Information related to the share value of the land on which the kilns were built and annual income for urban farmers and annual returns from dung for the animal raisers was also collected. Using descriptive statistics, budget calculation and Gini coefficient, the results indicated that renting the land to brick making kilns yields a 5-fold higher return than the rent for agriculture. Gini coefficient showed that the kiln owners had a more equal income distribution compared to farmers. To estimate emission of greenhouse gases (GHGs) and losses of N, P, K, Corg and DM from cow dung when used in brick making, samples of cow dung (loose and compacted) were collected from different kilns and analyzed for their N, P, K and Corg content. The procedure modified by the Intergovernmental Panel on Climate Change (IPCC, 1994) was used to estimate the gaseous emissions of cow dung and fuel wood. The amount of deforested wood was estimated according to the default values for wood density given by Dixon et al. (1991) and the expansion ratio for branches and small trees given by Brown et al. (1989). The data showed the monetary value of added N and P from cow dung was lower than for mineral fertilizers. Annual consumption of compacted dung (381 t DM) as biomass fuel by far exceeded the consumption of fuel wood (36 t DM). Gaseous emissions from cow dung and fuel wood were dominated by CO2, CO and CH4. Considering that Gerif land in urban Khartoum supports a multifunctional land use system, efficient use of natural resources (forest, dung, land and water) will enhance the sustainability of the UA and brick making activities. Adoption of new kilns with higher energy efficiency will reduce the amount of biomass fuels (cow dung and wood) used the amount of GHGs emitted and the threat to the few remaining forests.

Microbial response to restoration of tantalite mine soils in western Rwanda

Artisanal columbite-tantalite (coltan) mining has had negative effects on the rural economy in the great Lakes region of Africa through labor deficits, degradation and loss of farmland, food insecurity, high cost of living, and reduced traditional export crop production alongside secondary impacts that remotely affect the quality of air, water, soil, plants, animals, and human wellbeing. The situation is multifaceted and calls for a holistic approach for short and long-term mitigation of such negative effects. This study focuses on the effects of mine land restoration on soil microbiological quality in the Gatumba Mining District of western Rwanda. Some coltan mine wastelands were afforested with pine and eucalyptus trees while farmers directly cultivated others due to land scarcity. Farmyard manure (FYM) is the sole fertilizer applied on the wastelands although it is insufficient to achieve the desired crop yields. Despite this, several multi-purpose plants such as Tithonia diversifolia, Markhamia lutea, and Canavalia brasiliensis thrive in the area and could supplement FYM. The potential for these “new” amendments to improve soil microbial properties, particularly in the tantalite mine soils was investigated. The specific objectives of the study were to: (a) evaluate the effects of land use on soil microbial indices of the tantalite mine soils; (b) investigate the restorative effects of organic amendments on a Technosol; and (c) estimate the short-term N and P supply potential of the soil amendments in the soils. Fresh soils (0-20 cm) from an unmined native forest, two mine sites afforested with pine and eucalyptus forests (pine and eucalyptus Technosols), an arable land, and two cultivated Technosols (Kavumu and Kirengo Technosols) were analyzed for the physicochemical properties. Afterwards, a 28-day incubation (22oC) experiment was conducted followed by measurements of mineral N, soil microbial biomass C, N, P, and fungal ergosterol contents using standard methods. This was followed by a 12-week incubation study of the arable soil and the Kavumu Technosol amended with FYM, Canavalia and Tithonia biomass, and Markhamia leaf litter after which soil microbial properties were measured at 2, 8, and 12 weeks of incubation. Finally, two 4-week incubation experiments each were conducted in soils of the six sites to estimate (i) potential mineralizable N using a soil-sand mixture (1:1) amended with Canavalia and goat manure and (ii) P mineralization mixtures (1:1) of soil and anion exchange resins in bicarbonate form amended with Tithonia biomass and goat manure. In study one, afforestation increased soil organic carbon and total N contents in the pine and eucalyptus Technosols by 34-40% and 28-30%, respectively of that in the native forest soil. Consequently, the microbial biomass and activity followed a similar trend where the cultivated Technosols were inferior to the afforested ones. The microbial indices of the mine soils were constrained by soil acidity, dithionite-extractable Al, and low P availability. In study two, the amendments substantially increased C and N mineralization, microbial properties compared with non-amended soils. Canavalia biomass increased CO2 efflux by 340%, net N mineralization by 30-140%, and microbial biomass C and N by 240-600% and 240-380% (P < 0.01), respectively after four weeks of incubation compared with the non-amended soils. Tithonia biomass increased ergosterol content by roughly 240%. The Kavumu Technosol showed a high potential for quick restoration of its soil quality due to its major responses to the measured biological parameters. In study three, Canavalia biomass gave the highest mineralizable N (130 µg g-1 soil, P < 0.01) in the Kavumu Technosol and the lowest in the native forest soil (-20 µg g-1 soil). Conversely, the mineralizable N of goat manure was negative in all soils ranging from -2.5 µg N g-1 to -7.7 µg N g-1 soil except the native forest soil. However, the immobilization of goat manure N in the “cultivated soils” was 30-70% lower than in the “forest soils” signifying an imminent recovery of the amended soils from N immobilization. The mineralization of goat manure P was three-fold that of Tithonia, constituting 61-71% of total P applied. Phosphorus mineralization slightly decreased after four weeks of incubation due to sulfate competition as reflected in a negative correlation, which was steeper in the Tithonia treatment. In conclusion, each amendment used in this research played a unique role in C, N, and P mineralization and contributed substantially to microbial properties in the tantalite mine soils. Interestingly, the “N immobilizers” exhibited potentials for P release and soil organic carbon storage. Consequently, the combined use of the amendments in specific ratios, or co-composting prior to application is recommended to optimize nutrient release, microbial biomass dynamics and soil organic matter accrual. Transport of organic inputs seems more feasible for smallholder farmers who typically manage small field sizes. To reduce acidity in the soils, liming with wood ash was recommended to also improve P availability and enhance soil biological quality, even if it may only be possible on small areas. Further, afforestation with mixed-species of fast-growing eucalyptus and legume or indigenous tree species are suggested to restore tantalite mine wastelands. It is emphasized most of this research was conducted under controlled laboratory conditions, which exclude interaction with environmental variables. Also fine fractions of the amendments were used compared with the usual practice of applying a mixture of predominantly coarser fractions. Therefore, the biological dynamics reported in the studies here may not entirely reflect those of farmers’ field conditions.

Teoría de restricciones aplicada a la cadena de suministros en un operador logístico de productos farmacéuticos

En las instituciones hospitalarias es fundamental el tema relacionado con los medicamentos y dispositivos médicos para la atención del paciente, por lo tanto el mecanismo de adquisición y disponibilidad de éstos productos, ha llevado a la participación masiva de operadores logísticos (Outsoursing) interviniendo áreas de la cadena de suministros, desde el punto de fabricación con el producto terminado hasta la dispensación del medicamento o dispositivo médico, para que ser usado o administrado al paciente. Los operadores logísticos han emprendido una búsqueda de soluciones por medio de diferentes metodologías y estrategias que permitan entregar a tiempo en las farmacias hospitalarias, conservando las propiedades físicas y químicas de los medicamentos y dispositivos médicos, garantizando así la calidad de los productos. En ésta tesis se plantea una nueva alternativa de gestión de medicamentos y dispositivos médicos en un operador logístico de productos farmacéuticos a través de la teoría de restricciones (TOC), para emprender acciones que permitan analizar el sistema bajo esta metodología, intervenir de manera oportuna, impactar y estimular al personal a trabajar en la búsqueda del mejoramiento , aumentando a su vez la velocidad del flujo de operación en toda la cadena de suministros, basada no en el mejoramiento de los óptimos locales o de los subprocesos sino en la identificación de la verdadera restricción del sistema, permitiendo realizar un análisis más a fondo encontrando el conflicto raíz para mejorar el sistema a nivel global.

Bioinspired iron and manganese catalysts for the effective and selective oxidation of alkanes and alkenes

La gran eficiència, selectivitat i les condicions suaus exhibides per les reaccions que tenen lloc al centre actiu de les metal·looxigenases són la font d'inspiració per la present dissertació. Amb l'objectiu de dissenyar catalitzadors d'oxidació eficients hem fet ús de dues estratègies: la primera consisteix en el disseny de complexos amb baix pes molecular inspirats en aspectes estructurals de la primera esfera de coordinació del centre metàl·lic d'enzims de ferro i de manganès. Aquests complexos s'han estudiat com a catalitzadors en l'oxidació selectiva d'alcans i d'alquens fent servir oxidants "verds" com ara l'H2O2. La segona estratègia està basada en l'ús de la química supramolecular per tal de desenvolupar estructures moleculars auto-acoblades amb la forma i les propietats químiques desitjades. Concretament, la construcció de nanocontenidors amb un catalitzador d'oxidació incrustat a la seva estructura ens permetria dur a terme reaccions més selectives, tal com passa en les reaccions catalitzades per enzims.