FACULTY OF SCIENCE
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Item PHYSICOCHEMICAL STUDIES OF SOME TRIVALENT METAL β-DIKETONATES(1976-06) ADIMADO, A. A.Forty trivalent metal chelates of 2-thenoylacetone,2 thenoyltrifluoroacetone, 2-furoylacetone, 2-furoyltrifluoroacetone. benzoylacetone, benzoyltrifluoroacetone and nicotinoyltrifluoro— acetone (where metal(Hl) = Al, Crf Mn, Fe and Co) as well as some mixed ligand p-diketonate complexes of iron(IH), have been prepared and their spectroscopic and magnetic properties have been examined. Among the series of compounds studied, Al(fbd) Mn(fbd)3, AKtftbd), Co(tftbd)3, Cr(tffbd)3, Mn(tffbd)3, Co(tffbd)3, M(tbd)3, M(tfpybd)3 (where M = Al, Cr, Mn, Fe and Co ), Fe(bzac)2 (tftbd), Fe(tftbd)2(bzac), Fe(fbd)2(tbd)and Fe(tbd)2(fbd) have been investigated for the first time. The effects of 3-pyridyl, 2-thienyl, 2-furyl, phenyl and trifluoromethyl substituents have been discussed in relation to the lowest spin-allowed transition, п3- п4 and M-O,VC--O and VC--C-—C stretching vibrations. Substitution of a methyl group in 2,4-pentanedione - by a furyl ring, and a methyl group in 1-(2-furyl )-l,3-butanedione by a trifluoromethyl are found to strengthen the C---O and C —C—C and weaken the M—0 bonds of the chelate rings; while the 2-thienyl group shifts the M—O and C -- 0 to lower, and C---C to higher frequencies. The phenyl substituent, as expected, strengthens the M-O and C---C bonds and weakens the C--O bonds. The most sensitive M-0 stretching modes follow the order Co(lII) >A1(III) > Cr(III)> Mn (III) > Fe (III). However, the lowest spin-1llowed п3- п4 translation of the β-ketoenolate anion, although found to be metal sensitive, does not follow the same trend. Trifluoromethyl group substitution resulted in the bathochromic shift of the п3- п4 transitions. The ligand field energy parameters Dq,f (ligand)), B35 and β35 have been calculated and the following order of nephelauxetic effect in the ligands has been derived: Htffbd > Htbd > Hfbd > Hacac > Hbztfac > Htftbd > Hbzac > Htfpybd. While the spectrochemical series of the ligands depicted by the magnitude of f(ligand) parameter also follow:'.the orders tfpybd < bztfac < fbd < tffbd < tbd < acac ~ bzac < tftbd. The reflectance spectra and magnetic properties of these compounds revealed that they are very similar to the corresponding tris—(2,4—pentanedionato) metal(III) octahedral complexes.Item A GRAVITY PROFILE OF THE LOWER BENUE TROUGH OF NIGERIA(1976-06) ADIGHIJE, C. I.Gravity measurements were made along a roughly east-west profile across the lower Benue trough, with the main objectives of investigating the nature and configuration of the basement beneath the trough and determining the thickness of the sedimentary cover rocks. I87 gravity stations were established at 2-4km intervals and standard corrections were applied to the observed gravity values. A Bouguer gravity map of the whole Benue trough is compiled from the results of these measurements and data obtained from previous works. The map shows that the positive anomaly along the axis of the trough is a most prominent regional feature that extends over the whole length of the trough. The abrupt truncation of the positive anomalies along a NNE-SSE line may represent the Cretaceous continental margin. The axial positive is ascribed to the doming of the basement underlying relatively dense Albian Shales and their associated intermediate to basic intrusives along the trough axis as a result of tectonic processes. "Growth” of the positive anomaly towards the South is attributed to the basement being at a shallower depth in the lower Benue than in the upper Benue trough and to the probability that oceanic crust underlies the sediments at the southwestern end of the trough. The negative anomalies are due to thick sedimentary sequences which fill the flanks of the trough. The sediments are estimated to have a maximum thickness of 4.25km in the surveyed area of the lower Benue trough.Item AN INVESTIGATION OF SOME HORMONAL BASES FOR ABSCISSION IN COWPEA (VIGNA UNGUICULATA L. WALP.)(1977-05) ADESOMOJU, A. A.The Investigations carried out on the abscission problem in cowpea are reviewed. The Isolation 5 characterization 9 physiological roles, chemistry, biosynthesis and metabolism of the various groups of plant hormones are also reviewed. Using biological assays and combined gas-liquid chromatography- mass spectrometry (GC-MS, some of the hormones in the extensively purified acidic ethyl acetate extracts obtained from 2-day old and 6-day old cowpea fruits were examined. Biological assays indicated the presence of only Inhibitors in the 2-day old fruits but inhibitors as well as gibberellins and auxins were indicated to be present in the 6-day old fruits, GC-MS analysis of the extract from 2-day old fruits afforded the identification of the known inhibitors, abscisic acid and phaseic acid. 6’-hydroxymethyl abscisic acid was also identified in the extract and this is the first reported evidence that 6’-hydroxymethyl abscisic acid occurs naturally. Several plant hormones were identified (GC-MS analysis) in the extract from 6-day old fruits. These were abscisic acid, phaseic acid, dihydrophaseic acid,’1iso1dihydrophaseic acid, 6’-hydroxyinethy abscisic acid; gibberellins A4, A6, A8, ‘iso’ A8,and A20. Gibberellins A1,A5,and A29 were also believed to be probably present. Two components, believed to be two new gibberellins were also identified in the extract and were tentatively called gibberellins X and Y. Tentative structures were assigned to these two new gibberellins. Purified acidic ethyl acetate extract obtained from fruits that were over six days old was also analysed on the GC-MS. The result was essentially similar to that obtained for the extract from the 6-day old fruits. The crude acidic ethyl acetate extracts from 6-day old seeds and the fruit walls of the 6-day old fruits were also examined on the GC-MS. Several gibberellins were tentatively identified in the extract from the seeds but only one gibberellin could be identified in the extract from the fruit walls. The methyl esters of 16α-hydroxy, 17-hydroxy, and 16α, 17-dihydroxy derivatives of gibberellin A34 and the 16-epimers of the last two compounds were synthesized from gibberellin A4. This was done in order to correlate the structures that were tentatively assigned to the two new gibberellins with the natural compounds. The disparity in the hormonal contents of the 6-day old and 2-day old fruits is discussed in relation to the abscission problem in cowpea.Item AN X-RAY CRYSTALLOGRAPHIC STUDY OF SOME WOOD EXTRACTIVES(1967-02) ADEOYE, S. A.Item STUDIES IN THE THEORY OF MULTIPLIERS WITH APPLICATIONS TO SEMIGROUPS OF OPERATORS(1974-08) ADEWOYE, T. O.This thesis divides naturally into two parts. The first half is a study of the general theory of multipliers, while the second half deals with applications of the theory of multipliers to the theory of semigroups of operators defined on a Banach spice. We study the multiplier problem for an abstract Hilbert space li, and generalise to H certain important results established for La(G)-multipliers (Larsen [12], Hewitt and Ross [8]). A significant result of this study is the Identification of certain projection operators on L2(G) which are, in several respects. Like the translation operators on Ls (G). We also discuss the restricted multiplier problem for the Banach algebra L1(G) of all absolutely integrable complex-valued functions defined on a compact group G, and we obtain results which are analogous to those obtained by Brainerd and Edwards [1] for L1 (G), where G is a locally compact abelian group. In connection with, semigroups of operators, we discuss, in the context of various Banach spaces, the representation of the multipliers which arise semigroups of operators on these Banach spaces. In this respect, we extend the results of Hille and Phillips [10] proved for the circle group (and generalised to compact abelian groups by Olubummo A. and Babalola V.A. [13]) to certain Banach spaces which are not even function spaces. All these results put together provide a good link between the theory of multipliers for a Banach space and the theory of semigroups of operators on the Banach space.Item EXTRACTIVES FROM KHAYA SPECIES(1968-03) ADESOGAN, E. K.The chemistry of ß-furan-containing extractives obtained from trees of the family Meliaceae (and one tree from the family Rutaceae) is briefly reviewed and their biogenesis is discussed. In continuation of our study of the extractives from the family Meliaceae in this department, five species of the genus Khaya have been examined. The seed, timber, bark, root, and root-bark of three species, K. senegalensis, K. ivorensis, and K. grandifoliola, and the seeds of the two others, K. anthotheca, and K. nyasica were examined. The extracts are mainly the tetranortriterpenes with a ß-substituted furan, and about thirty of these were isolated and structures were assigned to nearly all of them. The known ones include khivorin, 7-deacetoxy-7-oxo-khivorin, 7-cleacetoxy-7-oxogedunin, methyl angolensate, mexicanolide, and deacetylgedunin. Those characterised and reported for the first time include khayasin, 6-deoxy-3ß-tigloyloxyswietenolide, 6-deoxy-3ß-benzoyloxyswietenolide, khayanthone, 3-deacetylkhivorin, 3-deacetyl-7-deacetoxy-7-oxokhivorin, methyl 6-hydroxyangolensate, grandifoliolin, 3-destigloyl-6-deoxyswietenine, 3-destigloyl-6- deoxy-3ß-acetoxyswietenine, 3ß-dihydrocarapin, and 3-destigloyl-6- deoxy-3ß, 12ß-diacetoxyswietenine. Others prepared before, but isolated as natural products for the first time include deoxy- andirobin, and 6-deoxyswietenolide. In addition two substances, A and B from K. ivorensis root-bark have structures proposed for them which are still to be confirmed, while not much is known of the structures of a few others especially methyl senegalensate. Most of these extracts contain glycosides and steroids, ß-sitosterol in particular. Of these only the steroid hormone 20ß-acetoxy-3-oxopregn-4-ene, a new compound, was sufficiently studied to be assigned a structure which was confirmed. The structural elucidation of these compounds have depended almost entirely on their spectral properties including those of their Chemical transformation products. Obviously physical properties played a great part especially in confirming a known compound by comparison of data. The co-occurence of some of these compounds have strengthened the argument for the biogenesis proposed. The chemotaxonomic implication was also discussed. A number of interesting reactions including some rearrangements are discussed and mechanism for some of them have been suggested.Item STUDIES ON THE CHARACTERISTIC pH OF HAEMOGLOBINS(1972-01) ADEOSUN, O. S.The thermodynamics of the azide binding reactions of the hybrids of human and canine haemoglobins (i.e. α2Aβ2Ca and α2Caβ2A) as well as the isolated α and ß polypeptide chains of human and canine haemoglobins have been studied at various pH's and temperatures. Plots of -ΔH° against pH, for all the species, show a distinct maximum. The pH at which the maximum value of - ΔH° occurs is termed the 'characteristic pH' (pH ch). From the results it is concluded that the value of pH ch for the haemoglobin tetramer is an average of the pH ch's of the separate α and ß polypeptide chains although: the form of the curve of -ΔH° against pH is a function of the tetramer and cannot be obtained by averaging -ΔH° values for the individual chains. The Bohr effect of the two hybrids has also been measured and compared with that of the parent haemoglobins. A study of the equilibrium reaction between oxyhaemoglobin and carbonmonoxide was carried out and the accompanying thermodynamic data assessed in terms of the mechanisms postulated for explaining ligand binding reactions of methaemoglobin.Item THE REACTIONS OF SOME ACTIVATED AROMATIC HALIDES WITH PIPERIDINS, AND N-BUTYLANINE IN DIPOLAR APROTIC AND DIPOLAR PROTIC SOLVENTS(1975) ADENLE, M. A.The reactions of 2-chloro-5-nitro pyridine with piperidine have been studied in acetone and in nethanol. In acetone, the rate constants are measured as a function of the anine concentration. In methanol, the Arrhenius parameters are obtained. In methanol, except for a very slight (almost negligible) downward trend of rate constants at very high concentration which is explained in terms of Charge - transfer complexes, there is no base catalysis and the observed rate constants are the rates of formation of the intermediate complex. The rates of reaction of 1-X-2, 4-dinitrobenzene (X=F, Cl) with piperidine and n-butylamine in methanol, acetone, and chloroform (stabilised and destabilised) have been measured as a function of the amine concentration. In acetone, the reactions of both substrates with piperidine show true base catalysis with K3/K2 > 50 in both cases. In Chloroform with n-butylamine, there is very little rate increase with increasing amine concentration. For both Substrates, K3/K2=3. This is explained in terms of hydrogen-bonding in the intermediate state. In methanol, the reaction of the chloro Substrate with piperidine gives a small linear increase of rate constants with increasing amine concentration; while for the fluoro substrate, the graph of rate constants against amine concentration gives a doubly sloped curve. This is due to some special unknown medium effects. In acetone, the reactions with n-butylamine give rather peculiar results. The chloro substrate appears to be more sensitive to catalysis by amine than the fluoro substrate - a Situation hitherto unknown. In general, for the reactions in methanol and Chloroform, there is not much base influence; while those in acetone are dependent on the base strength.Item SYNTHETIC STUDIES ON STEROIDAL ALKALOIDS(1966) ADEGOKE, E. A.In the first part of this thesis, a brief survey of the chemistry of veratramine viz. its occurrence, isolation and structural diagnosis is given. This part also includes a review of recent work on the stereochemistry and the synthetic work of other workers on the alkaloid. The main section describes three approaches to the synthesis of the C-Nor-D-homo ring system of the veratrum alkaloids. Howell and Taylor’s acetate diester 6(β-acetoxy-1 β:2αdi (methoxy carbonyl methyl)-9β-methyl-trans decalin prepared from 2:3:4:9:10:12- hexahydro-6-methoxy-12-methyl-2-oxophenanthrene was successfully cyclised to the potential intermediate 6(β -acetoxy-1 β:2α-( cyclopen- tan-3-one)-9-methyl-trans decalin. The pentanone was ring extended to give a solid substance which certainly contained the steroidal ring system of veratramine but which could not be obtained in the pure form. Attempts aimed at an easier preparation of the pentanone acetate by alkylating 1-oxo-6-ethoxy-8a-methyl-1,2,3,7,8, 8a hexahydro naphthalene with different alkylating agents were unsuccessful, the starting material being recovered in each case. In a second approach, 1-(2-cyanoethyl)-2-hydroxy naphthalene was converted to 2:3:4:9:10:12-hexahydro-6-methoxy-7-(3-bromo- propyl)-12-methyl-2-oxophenanthrene and 8-oxo-10a-methyl-1,2,3,4,5,6,8,9,10,10a-decahydro-1-oxa chrysene. The benzene nucleus of either intermediate was resistant to reduction and so they could not be used for further work. In the last attempt, 2-benzoyloxy-1,2,3,4,5,6,7,9,10,11,12,13 dodecahydro-12-methyl-7-oxophenanthrene was prepared starting with 2-naphthol and the tricyclic enone was successfully condensed with 2,2-ethylenedioxy-5-bromo pentan-2-one in the presence of potassium t-butoxide in t-butanol. The adduct was successively reduced, reacted with methyl magnesium bromide, deketalized y acetylated, ozonised and cyclised to give an oily substance which contained the veratramine steroidal nucleus as revealed by its U.V. spectrum. The oil did not crystallize. An oil which should probably crystallize more readily could be obtained if complete reduction of the original ansaturated adduct could be accomplished in the attempts some new compounds were prepared. These were mainly naphthalene, phenanthrene and hydrochrysene compounds. I.R U.V, or N.M.R. spectroscopic data were recorded for all the new compounds and for most of the known ones. Some structural formulae are repeated in the script, so as to aid the reader’s comprehension.Item KINETICS AND THERMODYNAMIC STUDIES OF NADP BINDING REACTIONS OF GENETIC VARIANTS OF HUMAN ERYTHROCYTE GLUCOSE 6-PHOSPHATE DEHYDROGENASE(1978-12) ADEDIRAN, S. A.Inherited Glucose-6-Phosphate dehydrogenase (G6PD) deficiency in humans results in hemolytic anaemia. The enzyme G6PD provides a crucial link in a series of biochemical reactions which occur in the red blood cell that leads to the steady state accumulation of NADPH, reduced glutathione by glutathione reductase, and the removal of potentially dangerous organic peroxides which, if not scanvenged, may result in the formation of radical species of oxygen which damage the energy generation system, which in turn may result in swelling, lysis and hemolytic anaemia. The objective of this thesis was to investigate the human variants of the enzyme G6PD in order to provide a better understanding of the molecular basis of the enzyme activity and factors affecting the onset of the human disease. Human Erythrocyte Glucose-6- Phosphate dehydrogenase has been known to occur in many genetic variants and the catalytic active enzyme of each variant are tetramers and dimers in acidic and alkaline solution respectively. The question then is whether there would be differences in the reactivities of these variants and whether there are differences in the reactivities of the two active forms of the enzyme from the same variant. A comparative analysis of the kinetic and thermodynamic studies of NADP+ binding reactions of these variants under controlled and well-defined experimental conditions of pH and ionic strength was therefore undertaken. The binding reaction of NADP+ to G6PD B+ was also studied as a function of ionic strength of the buffers in order to evaluate the effect of these variations in the buffer system on the co-operative interactions of the NADP+ binding sites on the enzyme. The findings show that there are two binding sites on each of the enzyme variants and these were identified as imidazolium groups of histidine and sulfhydryl groups. The logKm versus pH curves show a broad plateau between pH 6.7 and 8.2 interrupted by a sharp minimum at pH 7.1 for all the enzyme variants. An explanation of this behaviour in terms of co-operative ionization of groups on the enzyme and enzyme-substrate complex which may be linked to the association - dissociation behaviour of the enzyme is proposed. In agreement with G6P binding data, the plot of the enthalpy of the dissociation of enzyme - NADP+ complex against pH shows the shape of a two U—shaped curves consistent with the existence of a tetrameric form of enzyme at acidic pH and dimeric form at alkaline pH. A similar plot of the activation energy of the reaction for each variant shows a consistent decrease of the activation energy with increase in pH, the activation energy at the pH 5.8 being almost halved at the alkaline pH of 9.0, This behaviour is explained to arise from the dimer enzyme being more reactive than the tetramer. There are two schools of thought about the existence and nature of cooperativity among the NADP+ binding sites on G6PD subunits. The study reported in this thesis has unequivocally solved the controversy between the two schools. It is now established that the tetrameric form of the enzyme shows no Cooperativity while the dimeric form is cooperative. The disagreement between the two schools of thought has been explained in the variable experimental conditions used by the workers in the two schools. We have shown that an experimental condition that favours tetramer formation therefore favours non-cooperativity while a condition that favours dimer formation favours cooperativity. The inhibition study by primaquine phosphate shows a complex interaction of this effector with G6PD. There is activation of the G6PD activity at low effector concentration and inhibition at high concentration. This interaction may be due to oxidation of NADPH at low primaquine concentration resulting in generation of more NADP+ which increases the activity of the enzyme. Such a situation might account for the increased hemolysis in variant subjects with low Artracellular NADPH concentration which will result in low level of reduced glutathione. Reduced glutathione is necessary for the maintenance of the integrity of the red cells.