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DESULPHURIZATION OF NIGERIAN LAFIA COAL FOR METALLURGICAL COKE PREPARATION
(1988-01) ADERONPE, W. I. A.
The Government-owned integrated iron and steel plant under construction in Ajaokuta has been designed to operate through the blast-furnace process. The blast-furnace requires metallurgical coal. It therefore became necessary and relevant to the national economy to scientifically work on Nigerian coals with a view to using same as metallurgical coal. Lafia coal is the only Nigerian coal that produces coke lump after dry distillation (carbonization). The property of coke- ability therefore attracted attention towards Lafia coal. The main interest was to so prepare the coal that as much as possible of it will be usable for metallurgical coke preparation for use in Ajaokuta blast-furnace. Lafia coal was subjected to chemical characterization and petrological studies. It became clear that it was high in ash and sulphur. Silicates, pyrites and carbonates of various elements constituted the inorganic mineral inclusions. Analytical data gave the sulphur varieties in Lafia coal to be organic (0.1 - 0.7%), pyritic (1.4 - 4.4%) and sulphate (0.01 - 0.07%). Pyritic sulphur which predominates in Lafia coal can be removed by physical means. Chemical desulphurization which is reducto-oxidative type of chemical reaction impares coal cokeability. A plunge was thus made for physical desulphurization techniques to bring down the total sulphur in Lafia coal to the level that will make it acceptable as a metallurgical coal with regards to its sulphur content. Trace elements in Nigerian coal ash determined using the Atomic Absorption Spectrophotometer (AAS) and confirmed with the Inductively Coupled Plasma Emission Spectrophotometer (ICPES) showed that the relative abundance of the elements in the coals depended on the biogeo-chemistry of the area of the deposit as follows: Lafia coal; F>Zn>Mn»V Cr>Ni>Cu>B>Pb>Ca>Be>Mo>Cd>Hg Enugu coal; B>Mn>V F>Cr>Zn>Cu>Pb Ni>Co>Be>Mo>Hg Okaba coal; Mn»B»V>Cr>Cu>Pb>F=Ni>Zn Co>Be>Mo>Hg Trace element content of coal was considered in connection with the impact of coal utilization on the environment. From the study it was concluded that either the wet concentrating table or the froth flotation method could be used to substantially desulphurize Lafia coal to meet the requirement of metallurgical coal.
DEVELOPMENT OF RESIN-BOUND REAGENTS FOR ANALYSIS OF CARBOXYLIC ACIDS AND AMINES
(1993-12) ADEWUYI, G. O.
Resin-bound-reagents made up of ionically-bound 2- naphthalene-methanol and covalently bound and sodium-benzoxazole- 2-sulfonate have been synthesized and utilized as analytical reagents for the pre-chromatographic derivatization of fatty acids (i.e. acetic, lauric, capric, hexanoic, octanoic, nonanoic, palmitic, docosanoic linoleic), 1° and 2° aliphatic amines and amino acids respectively. The reagents have been designed to contain fluorescent moieties attached to the anionic and cationic resin backbones through sulfonated ester linkages. These moieties imparted UV and FL detector properties to the final derivatives. The derivatization reactions were performed before the thin- layer Chromatographie separations. Standards we,-e prepared and were used in monitoring the extent of reactions on the resin support. The derivatives were chromatographed and fluorescent spots were observed under UV light. These solid phase derivatizations have led to preliminary investigation of these two functionalities before embarking on instrumentation analysis such as high performance liquid chromatography with UV or fluorescence detection and HPLC-MS Identification.
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.
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.
METAL(II) TETRAFLUOROBORATE COMPLEXES OF SOME DICARBOXYLIC ACID HYDRAZIDES
(1990) ADENIYI, A. A.
Eighty-eight divalent metal complexes derived from dihydrazides of oxalic, malonic, succinic, adipic, phthalic and terephthalic acids, with manganese( 11), cobalt(ll), nickel(ll), copper(IJ), zinc(ll), cadmium(ll), mercury(ll) and magnesium tetrafluoroborates have been prepared. The effect of 1:1 and 1:2 metal to ligand reactant ratios have been examined. The complexes have been characterized on the basis of their analytical data, magnetic susceptibility, electronic and IR spectral studies as well as conductance measurements. Reactions involving 1:1 and 1:2 metal to ligand ratios gave complexes with different metal to ligand stoichiometry in most cases. It is evident, from the analytical data, that complexes precipitated out mostly with 1:2 and 1:3 metal to ligand stoichiometry. However, complexes of oxalic dihydrazide with Cu (II) and Hg (II), succinic dihydrazide with Co (II), Ni(ll), Zn(ll) and Mg prepared using a 1:1 molar reactant ratio contained one and a half moles of ligands. Similarly, complexes of Mn(ll), Ni(ll) and Hg(ll) prepared using a 1:2 molar ratio of metal salt to adipic dihydrazide contained one and a half moles of adipic dihydrazide. Nevertheless, reactions involving 1:1 and 1:2 molar reactant ratios gave the same set of compounds in phthalic dihydrazide with Co(ll), Ni(ll) and Zn(ll) tetrafluoroborates respectively. Likewise the complexes of adipic and malonic dihydrazides with Zn(BF4)2 .6H2O4 and Cd(BF4)2 .7H2O respectively. The complexes have poor solubilities in methanol, ethanol, acetone, nitrobenzene, nitromethane, benzene, hexane, aceto- nitrile, dimethylformamide, dimethylsulfoxide and water. But the complexes of inanganese( 11), cobalt(ll), zinc(ll) and cadmium(II) with oxalic, malonic, succinic and adipic dihydrazides were found to be soluble in water. Similarly, nickel(11), CO ppe-f (11) and magnesium complexes of malonic and succinic dihydrazides were soluble in water, so also is the complex of mercury(ll) with adipic dihydrazide. In addition, the complexes of succinic dihydrazide, with manganesef11) and cadmium(ll) tetrafluoroborates were soluble in dimethylsulfoxide. The infrared spectra indicate that the bonding sites in these compounds are the carbonyl oxygen and the amino or amide nitrogens. The electronic and magnetic data of the complexes of manganese( 11), cobalt(ll), nickel(ll) and copper(ll) at room temperature suggested that they assume octahedral geometry. Generally, for a given ligand, the 1:2 complex has a lower magnetic moment than the 1:3 complex. The Variation of the moments with chain length does not appear to be systematic at room temperature. However, the magnetic moments for the Zn (11), Cd(II), Hg(ll) and Mg indicates that they are diamagnetic with some evidence of polarization paramagnetism. The conductance data of the complexes that were soluble in water and dimethylsulfoxide revealed 1:2 type electrolytes.
PHYTOCHEMICAL AND PHARMACOLOGICAL EXAMINATION OF ENTANDROPHRAGMA ANGOLENSE AND CRYPTOLEPIS SANGUINOLENTA
(1994-03) KOLAWOLE, A. J.
Dried, pulverized stem bark and the root bark of Entandrophragma anqolense were separately extracted with methanol. The crude methanolic extract of the stem and root bark of E. anqolense were subjected to column fractionation and purification. This exercise afforded the Isolation of methyl angolensate, 2.26% yield from the stem bark and 0.27% yield from the root bark. The effect of the crude methanolic stem bark extract was investigated on indomethacin-induced gastric ulcer in rats. Its effect was dose-dependent, doses ranging from 0.4 to 1.6 gkg-1 body weight (BW) produced significant effect (P < 0.05). At the highest dose used (1.6gkg-1 BW), complete inhibition of ulceration occurred. Toxicity study showed that the extract was not toxic when doses ranging from 20-200gkg-1 BW was administered to experimental rats. It was established that methyl angolensate is the major anti- ulcer principle present in the methanolic extract of the stem bark of E. angolensate. Methyl angolensate produced a dose-related inhibition of gastric ulceration induced by indomethacin, 40mgkg BW being more effective than 40mgkg-1 BW of propanolol. 80mgkg-1 BW of methyl angolensate completely inhibited gastric ulceration. Methyl angolensate also significantly reduced gastric acid secretion induced by histamine and carbachol (1.0mgkg-1 BW). Thus we confirmed that methyl angolensate produces its anti-ulcer activity through inhibition of gastric acid secretion. The roots of Cryptolepis sanquinolenta were extracted with methanol. Column fractionation of the methanolic extract afforded the Isolation of a new benzocarboline alkaloid labelled (CS-1) melting point 272-274°C. Spectroscopic analysis of CS-1 including the infra-red (IR), 13 ultra-violet (UV), mass spectrum (MS), proton and C-nuclear magnetic spectroscopy were reported. This new alkaloid exhibited anti-microbial activity on five pathogenic organisms. The in-vivo anti-malarial study of the aqueous extract of the roots of sanguinolenta was done on Plasmodium yoeli nigeriensis in mice. Anti-malarial activity of the extract was determined by examining the blood schizontocidal action in established infection using chloroquine as Standard drug for comparison. The extract showed a dose-dependent effect against the malarial parasite.
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.
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.
AN X-RAY CRYSTALLOGRAPHIC STUDY OF SOME WOOD EXTRACTIVES
(1967-02) ADEOYE, S. A.