Spectral and Structural Studies of Transition Metal Complexes of Thiosemicarbazones Containing Ring Incorporated at N(4)-position

The thesis is an introduction to evaluate the coordination behaviour of a few compounds of our interest. The crucial aim of these investigations was to synthesize and characterize some transition metal complexes using the ligands benzaldehyde, 2-hydroxybenzaldehyde and 4-methoxybenzaldehyde N(4)-ring incorporated thiosemicarbazones.The study involves a brief foreword of the metal complexes of thiosemicarbazones including their bonding, stereochemistry and biological activities.The different analytical and spectroscopic techniques used for the analysis of the ligands and their complexes are discussed.It also deals with the synthesis and spectral characterization of the thiosemicarbazones and single crystal X-ray diffraction study of one of them.Chapter 3 describes the synthesis, spectral characterization, single crystal X-ray diffraction studies of copper(ll) complexes with ONS/NS donor thiosemicarbazones. Chapter 4 deals with the synthesis, spectral characterization and single crystal X-ray diffraction studies of nickel(II) complexes. Chapter 5 contains the synthesis, structural and spectral characterization of the cobalt(III) complexes. Chapters 6 and 7 include the synthesis, structural and spectral characterization of zinc(II) and cadmium(ll) complexes with ONS/NS donor thiosemicarbazones.

The Ratios of Carbon, Nitrogen, and Phosphorus in a Wetland Coastal Ecosystem of Southern India

The fertility of the coastal and estuarine waters is of great concern because of its influence on the productivity of these waters. Seasonal variations in the distribution of organic carbon, total nitrogen and total phosphorus in the sediments of Kuttanad Waters, a part of the tropical Cochin Estuary on the south west coast of India, are examined to identify the contribution of sediments to the fertility of the aquatic systems. The adjoining region has considerable agricultural activity. The fresh water zones had higher quantities of silt and clay whereas the estuarine zone was more sandy. Organic carbon, total phosphorus and total nitrogen were higher in the fresh water zones and lower in the estuarine zones. Total phosphorus and organic carbon showed the lowest values during monsoon periods. No significant trends were observed in the seasonal distributions of total nitrogen. Ratios of C/N, C/P and N/P, and the phosphorus and nitrogen content indicate significant modification in the character of the organic matter. Substantial amounts of the organic matter can contribute to reducing conditions and modify diagenetic processes

Fractionation and bioavailability of phosphorus in a tropical estuary, Southwest India

Phosphorus fractionation was employed to find the bioavailability of phosphorus and its seasonal variations in the Panangad region of Cochin estuary, the largest estuarine system in the southwest coast of India. Sequential extraction of the surficial sediments using chelating agents was taken as a tool for this. Phosphate in the water column showed seasonal variations, with high values during the monsoon months, suggesting external runoff. Sediment texture was found to be the main factor influencing the spatial distribution of the geochemical parameters in the study region. Similarly, total phosphorus also showed granulometric dependence and it ranged between 319.54 and 2,938.83 μg/g. Calcium-bound fraction was the main phosphorus pool in the estuary. Significant spatial variations were observed for all bioavailable fractions; iron-bound inorganic phosphorus (5.04–474.24 μg/g), calcium-bound inorganic phosphorus (11.16–826.09 μg/g), and acidsoluble organic phosphorus (22.22–365.86 μg/g). Among the non-bioavailable phosphorus, alkalisoluble organic fraction was the major one (51.92– 1,002.45 μg/g). Residual organic phosphorus was K. R. Renjith (B) · N. Chandramohanakumar · M. M. Joseph Department of Chemical Oceanography, School of Marine Sciences, Cochin University of Science and Technology, Kochi 682016, Kerala, India e-mail: renjithaqua@gmail.com comparatively smaller fraction (3.25–14.64% of total). The sandy and muddy stations showed distinct fractional composition and the speciation study could endorse the overall geochemical character. There could be buffering of phosphorus, suggested by the increase in the percentage of bioavailable fractions during the lean premonsoon period, counteracting the decreases in the external loads. Principal component analysis was employed to find the possible processes influencing the speciation of phosphorus in the study region

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.

Effects of fertility management strategies on phosphorus bioavailability in four West African soils

Low phosphorus (P) in acid sandy soils of the West African Sudano-Sahelian zone is a major limitation to crop growth. To compare treatment effects on total dry matter (TDM) of crops and plant available P (P-Bray and isotopically exchangeable P), field experiments were carried out for 2 years at four sites where annual rainfall ranged from 560 to 850 mm and topsoil pH varied between 4.2 and 5.6. Main treatments were: (i) crop residue (CR) mulch at 500 and 2000 kg ha^-1, (ii) eight different rates and sources of P and (iii) cereal/legume rotations including millet (Pennisetum glaucum L.), sorhum [Sorghum bicolor (L.) Moench], cowpea (Vigna unguiculata Walp.) and groundnut (Arachis hypogaea L.). For the two Sahelian sites with large CR-induced differences in TDM, mulching did not modify significantly the soils' buffering capacity for phosphate ions but led to large increases in the intensity factor (C_p) and quantity of directly available soil P (E_1min). In the wetter Sudanian zone lacking effects of CR mulching on TDM mirrored a decline of E_1min with CR. Broadcast application of soluble single superphosphate (SSP) at 13 kg P ha^-1 led to large increases in C_p and quantity of E_1min at all sites which translated in respective TDM increases. The high agronomic efficiency of SSP placement (4 kg P ha^-1) across sites could be explained by consistent increases in the quantity factor which confirms the power of the isotopic exchange method in explaining management effects on crop growth across the region.

Efficient phosphorus application strategies for increased crop production in sub-Saharan West Africa

Comparable data are lacking from the range of environments found in sub-Saharan West Africa to draw more general conclusions about the relative merits of locally available rockphosphate (RockP) in alleviating phosphorus (P) constraints to crop growth. To fill this gap, a multi-factorial field experiment was conducted over 4 years at eight locations in Niger, Burkina Faso and Togo. These ranged in annual rainfall from 510 to 1300 mm. Crops grown were pearl millet (Pennisetum glaucum L.), sorghum (Sorghum bicolor (L.) Moench) and maize (Zea mays L.) either continuously or in rotation with cowpea (Vigna unguiculata Walp.) and groundnut (Arachis hypogaea L.). Crops were subjected to six P fertiliser treatments comprising RockP and soluble P at different rates and combined with 0 and 60 kg N ha^-1. For legumes, time trend analyses showed P-induced total dry matter (TDM) increases between 28 and 72% only with groundnut. Similarly, rotation-induced raises in cereal TDM compared to cereal monoculture were only observed with groundnut. For cereals, at the same rate of application, RockP was comparable to single superphosphate (SSP) only at two millet sites with topsoil pH-KCl <4.2 and annual average rainfall >600 mm. Across the eight sites NPK placement at 0.4 g P per hill raised average cereal yields between 26 and 220%. This was confirmed in 119 on-farm trials revealing P placement as a promising strategy to overcome P deficiency as the regionally most growth limiting nutrient constraint to cereals.

Phosphorus placement an acid arenosols of the West African Sahel

Phosphorus (P) deficiency is a major constraint to pearl millet (Pennisetum glaucum L.) growth on acid sandy soils of the West African Sahel. To develop cost-effective fertilization strategies for cash poor farmers, experiments with pearl millet were conducted in southwestern Niger. Treatments comprised single superphosphate hill-placed at rates of 1, 3, 5 or 7 kg P ha^−1 factorially combined with broadcast P at a rate of 13 kg ha^−1. Nitrogen was applied as calcium ammonium nitrate at rates of 30 and 45 kg ha^−1. At low soil moisture, placement of single superphosphate in immediate proximity to the seed reduced seedling emergence. Despite these negative effects on germination, P placement resulted in much faster growth of millet seedlings than did broadcast P. With P application, potassium nutrition of millet was improved and seedling nitrogen uptake increased two- to three-fold, indicating that nitrogen was not limiting early millet growth. Averaged over the 1995 and 1996 cropping seasons, placed applications of 3, 5 and 7 kg P ha^−1 led to 72%, 81% and 88% respectively, of the grain yield produced by broadcasting 13 kg P ha^−1. Nitrogen application did not show major effects on grain yield unless P requirements were met. A simple economic analysis revealed that the profitability of P application, defined as additional income per unit of fertilizer, was highest for P placement at 3 and 5 kg ha^−1.

Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.

Effects of phosphorus and water stress on shoot and root growth and on mycorrhization of different pearl millet (Pennisetum glaucum (L.) R. Br.) varieties from West Africa

This research work aimed at investigating the physiological mechanisms of tolerance of pearl millet to low soil Phosphorus availability and drought under the Sahelian conditions.

Syllable structures is modulating the optimal viewing position in visual word recognition. 'La estructura silábica modula la posición óptima de visualización en el reconocimiento visual de palabras'.

Resumen en español. Resumen basado en el de la publicación

Building Professional Capacity Aiming to Improve the Educational Position of Migrant Children : a reflection on the Sirius network activities

Resumen basado en el de la publicaci??n

How do Scrabble players encode letter position during reading?

Resumen tomado de la publicaci??n

Ocular vestibular evoked myogenic potentials (oVEMP) using air conducted sound: Effect of body position on threshold

The primary objective of this research study is to determine if various body positions for ocular vestibular evoked myogenic potential (oVEMP) testing demonstrate differentiation of the saccule and utricle through threshold responses.

Verification of computed tomographic estimates of cochlear implant array position: A micro-CT and histological analysis

We examine the efficacy two volume spatial registration of pre and postoperative clinical computed tomography (CT) imaging to verify post-operative electrode array placement in cochlear implant (CI) patients. To measure the degree of accuracy with which the composite image predicts in-vivo placement of the array, we replicate the CI surgical process in cadaver heads. Pre-operative, post-operative, micro CT imaging and histology are utilized for verification.