The chemistry of the wattle tannins
- Authors: Roux, David Gerhardus
- Date: 1953
- Subjects: Tannin plants , Tannins , Wattles (Plants)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
- Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
- Full Text:
- Date Issued: 1953
- Authors: Roux, David Gerhardus
- Date: 1953
- Subjects: Tannin plants , Tannins , Wattles (Plants)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
- Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
- Full Text:
- Date Issued: 1953
Some measurements of the conductivities of dilute potassium chloride solutions
- Authors: Faure, Abraham
- Date: 1954
- Subjects: Potassium chloride
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4471 , http://hdl.handle.net/10962/d1011787
- Description: A constant temperature room has been constructed in which the thermoregulator is controlled by a temperature-sensitive resistance. A thermostat has been constructed in which the 0 temperature is controlled to within 0.001°C. A precision conductance bridge has been built in a very convenient form. Improvements include the replacement of the telephone as null detector by a cathode ray oscilloscope, and the use of a resistance-capacity phase-shift oscillator, which gives a good wave-form. An automatic recycling conductance water still has been built which regularly gives water with a conductivity less than 0.09 micromhos per cm. The conductivities of dilute KCl solutions have been measured, taking special care to prevent errors due to the adsorption of KCl on the surface of glass. Two cells were used for these measurements : a modified Jones cell, and a special conductimetric titration cell. The modified Jones cell has given results in good agreement with the generally-accepted values. The results of the conductimetric titration cell do not agree well with the generally-accepted values; the greatest difference (for the most dilute solution) is 0.4%. The reason for this is not known.
- Full Text:
- Date Issued: 1954
- Authors: Faure, Abraham
- Date: 1954
- Subjects: Potassium chloride
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4471 , http://hdl.handle.net/10962/d1011787
- Description: A constant temperature room has been constructed in which the thermoregulator is controlled by a temperature-sensitive resistance. A thermostat has been constructed in which the 0 temperature is controlled to within 0.001°C. A precision conductance bridge has been built in a very convenient form. Improvements include the replacement of the telephone as null detector by a cathode ray oscilloscope, and the use of a resistance-capacity phase-shift oscillator, which gives a good wave-form. An automatic recycling conductance water still has been built which regularly gives water with a conductivity less than 0.09 micromhos per cm. The conductivities of dilute KCl solutions have been measured, taking special care to prevent errors due to the adsorption of KCl on the surface of glass. Two cells were used for these measurements : a modified Jones cell, and a special conductimetric titration cell. The modified Jones cell has given results in good agreement with the generally-accepted values. The results of the conductimetric titration cell do not agree well with the generally-accepted values; the greatest difference (for the most dilute solution) is 0.4%. The reason for this is not known.
- Full Text:
- Date Issued: 1954
The chemistry of naturally occurring long chain unsaturated compounds
- Authors: Silk, M H
- Date: 1954
- Subjects: Compounds, Unsaturated
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4518 , http://hdl.handle.net/10962/d1014332
- Description: [From Introduction, p. 3] Raw marine oils are subject to considerable variation in composition with season and are moreover very unbalanced oils for direct use in the paint industry. Further refining is undertaken chiefly by Messrs Marine Oil Refiners of Africa Ltd., whose factory is situated at Simonstown. In their plant marine oils and others are treated by the Solexol process involving counter current extraction of the oil with liquid propane in a tower over which a temperature gradient is maintained. The process achieves the removal of a large proportion of the relatively saturated glycerides, the natural antitioxidants, and the relatively highly unsaturated components, all of which are detrimental to the eventual formation of good paint films. The segregated marine oil from the Solexol process is then bodied or polymerised at high temperatures to yield a "drying oil" which is used as a substitute for bodied linseed oil in paints. The chemical reactions taking place during the polymerisation and drying of these oils are of an exemely complex nature, and for their understanding it is necessary to have an accurate knowledge of the chemical nature of the component fatty acids in the natural glycerides ... The term "marine oils" in this work should be understood to mean marine fish body oils, marine mammal oils being excluded from consideration.
- Full Text:
- Date Issued: 1954
- Authors: Silk, M H
- Date: 1954
- Subjects: Compounds, Unsaturated
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4518 , http://hdl.handle.net/10962/d1014332
- Description: [From Introduction, p. 3] Raw marine oils are subject to considerable variation in composition with season and are moreover very unbalanced oils for direct use in the paint industry. Further refining is undertaken chiefly by Messrs Marine Oil Refiners of Africa Ltd., whose factory is situated at Simonstown. In their plant marine oils and others are treated by the Solexol process involving counter current extraction of the oil with liquid propane in a tower over which a temperature gradient is maintained. The process achieves the removal of a large proportion of the relatively saturated glycerides, the natural antitioxidants, and the relatively highly unsaturated components, all of which are detrimental to the eventual formation of good paint films. The segregated marine oil from the Solexol process is then bodied or polymerised at high temperatures to yield a "drying oil" which is used as a substitute for bodied linseed oil in paints. The chemical reactions taking place during the polymerisation and drying of these oils are of an exemely complex nature, and for their understanding it is necessary to have an accurate knowledge of the chemical nature of the component fatty acids in the natural glycerides ... The term "marine oils" in this work should be understood to mean marine fish body oils, marine mammal oils being excluded from consideration.
- Full Text:
- Date Issued: 1954
Measurements of the solubilities of some silver halides in water by electrical methods
- Authors: Malan, George McPherson
- Date: 1955
- Subjects: Silver halides -- Solubility , Silver halides -- Analysis , Conductometric analysis , Potentiometry , Silver halides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4515 , http://hdl.handle.net/10962/d1013502
- Description: [Introduction, p. 3] The solubilities of the silver halides cannot be determined by the conventional methods of analytical chemistry because they are too sparingly soluble (of the order 1 x 10⁻⁵ to 1 x 10⁻⁶ g . equiv./1. at 25°C.) However, electrical, and to a lesser extent optical methods, are admirably suited because of their greater sensitivity. The conductometric and potentiometric methods are the two most important electrical techniques for the measurement of the solubilities of sparingly soluble salts, and are the ones employed in this research. There are large discrepancies between the published values for the solubility of silver chloride. Results obtained by the conductometric and potentiometric methods disagree. In addition, figures quoted by independent authors using the same method differ by as much as 15%.
- Full Text:
- Date Issued: 1955
- Authors: Malan, George McPherson
- Date: 1955
- Subjects: Silver halides -- Solubility , Silver halides -- Analysis , Conductometric analysis , Potentiometry , Silver halides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4515 , http://hdl.handle.net/10962/d1013502
- Description: [Introduction, p. 3] The solubilities of the silver halides cannot be determined by the conventional methods of analytical chemistry because they are too sparingly soluble (of the order 1 x 10⁻⁵ to 1 x 10⁻⁶ g . equiv./1. at 25°C.) However, electrical, and to a lesser extent optical methods, are admirably suited because of their greater sensitivity. The conductometric and potentiometric methods are the two most important electrical techniques for the measurement of the solubilities of sparingly soluble salts, and are the ones employed in this research. There are large discrepancies between the published values for the solubility of silver chloride. Results obtained by the conductometric and potentiometric methods disagree. In addition, figures quoted by independent authors using the same method differ by as much as 15%.
- Full Text:
- Date Issued: 1955
A conductimetric investigation of phenomena in extremely dilute aqueous solutions
- Authors: Faure, Pierre Knobel
- Date: 1957
- Subjects: Adsorption , Solution (Chemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4524 , http://hdl.handle.net/10962/d1014891
- Description: 1. The apparatus used in this investigation is fully described, and a new method is outlined for the calibration of bridge resistances "in situ". 2. A chart is given for the accurate correction of weights in air to weights in vacuum for a range of temperatures extending from 10° to 28°C, and for pressures from 690 to 730 mm. 3. An automatic recycling still has been designed for the continuous production of "ultra-pure" water. This still is capable of delivering daily, in routine operation, 16 l. of water of conductivity less than 100 nm/cm after aeration with "C0₂- and NH₃-free" air. 4. A very soluble layer appears to form on the surface of' glass when it is dried; this layer is readily removed on contact with water. 5. The removal of carbon dioxide and of ammonia from aqueous solution by aeration with an indifferent gas has been fully investigated, and it has been shown that these gases can be completely eliminated by such a process. Whereas the carbon dioxide is removed fairly rapidly, however, the ammonia, whether present alone or together with carbon dioxide, only goes out of solution rather slowly. 6. It has been shown that ammonia is adsorbed from aqueous solution on the glass walls of the cell. 7. There does not appear to be any ammonium bicarbonate in the residual impurity left in the "ultra-pure" water obtained from the still; the impurity can, in fact, be regarded as neutral salt with sufficient accuracy for most purposes. 8. The resistance change which accompanies any variation in the rate of bubbling of the stirring gas through the water has been investigated, but no solution has been found as to the cause of this change. 9. A comparison has been made of the efficiency of different gases for stirring purposes, and it seems that, for general work, nitrogen is by far the most suitable of the common gases. 10. The extrapolation to be used for converting resistances to their values at infinite frequency appears ...
- Full Text:
- Date Issued: 1957
- Authors: Faure, Pierre Knobel
- Date: 1957
- Subjects: Adsorption , Solution (Chemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4524 , http://hdl.handle.net/10962/d1014891
- Description: 1. The apparatus used in this investigation is fully described, and a new method is outlined for the calibration of bridge resistances "in situ". 2. A chart is given for the accurate correction of weights in air to weights in vacuum for a range of temperatures extending from 10° to 28°C, and for pressures from 690 to 730 mm. 3. An automatic recycling still has been designed for the continuous production of "ultra-pure" water. This still is capable of delivering daily, in routine operation, 16 l. of water of conductivity less than 100 nm/cm after aeration with "C0₂- and NH₃-free" air. 4. A very soluble layer appears to form on the surface of' glass when it is dried; this layer is readily removed on contact with water. 5. The removal of carbon dioxide and of ammonia from aqueous solution by aeration with an indifferent gas has been fully investigated, and it has been shown that these gases can be completely eliminated by such a process. Whereas the carbon dioxide is removed fairly rapidly, however, the ammonia, whether present alone or together with carbon dioxide, only goes out of solution rather slowly. 6. It has been shown that ammonia is adsorbed from aqueous solution on the glass walls of the cell. 7. There does not appear to be any ammonium bicarbonate in the residual impurity left in the "ultra-pure" water obtained from the still; the impurity can, in fact, be regarded as neutral salt with sufficient accuracy for most purposes. 8. The resistance change which accompanies any variation in the rate of bubbling of the stirring gas through the water has been investigated, but no solution has been found as to the cause of this change. 9. A comparison has been made of the efficiency of different gases for stirring purposes, and it seems that, for general work, nitrogen is by far the most suitable of the common gases. 10. The extrapolation to be used for converting resistances to their values at infinite frequency appears ...
- Full Text:
- Date Issued: 1957
A statistical study of the errors involved in the sampling and chemical analysis of soils and plants, with particular reference to citrus and pineapples
- Steyn, Willem Johannes Abraham
- Authors: Steyn, Willem Johannes Abraham
- Date: 1958
- Subjects: Soil chemistry , Plants -- Analysis , Soils -- Analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4506 , http://hdl.handle.net/10962/d1013291
- Description: 1. Accurate and reproducible methods for the determination of N and acid- extractable P in soils are described. The variations in N, P, and K found by intensive sampling of three different soil types are presented. 3. Suggestions for the adequate sampling of soils for various purposes arc given. 4. A study is presented of the preparative stages in leaf analysis (washing, drying, grinding and storage) as applied to citrus and pineapple leaf material. Likely errors are pointed out and procedures whereby these may be minimised are described. 5. A reliable wet-ashing procedure for obtaining leaf solutions is described. 6. Accurate and reproducible methods for the determination of total N, P,. K, Ca, Mg, Na, Fe, Mn, Zn and Cu in citrus and pineapple leaves are presented. 7. It is shown that diurnal variations in nutrient concentrations occur in citrus and pineapple leaves. 8. The variations in N, P, K, Ca, Mg, Na, Fe, Mn, Zn and Cu, occurring from tree to tree in 3 different Navel orange blocks are presented. It is shown that if all these elements are to be represented . to within 10% of the mean values on a 19 : 1 probability level, all the trees in the blocks would have to be sampled. Reasonable sampling procedures for various purposes are suggested. 9. The variations in N, P, K, Ca, Mg, Fe, Mn, Zn and Cu, occurring in 3 different Cayenne pineapple plantations are presented and described. Suitable sampling procedures are suggested.
- Full Text:
- Date Issued: 1958
- Authors: Steyn, Willem Johannes Abraham
- Date: 1958
- Subjects: Soil chemistry , Plants -- Analysis , Soils -- Analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4506 , http://hdl.handle.net/10962/d1013291
- Description: 1. Accurate and reproducible methods for the determination of N and acid- extractable P in soils are described. The variations in N, P, and K found by intensive sampling of three different soil types are presented. 3. Suggestions for the adequate sampling of soils for various purposes arc given. 4. A study is presented of the preparative stages in leaf analysis (washing, drying, grinding and storage) as applied to citrus and pineapple leaf material. Likely errors are pointed out and procedures whereby these may be minimised are described. 5. A reliable wet-ashing procedure for obtaining leaf solutions is described. 6. Accurate and reproducible methods for the determination of total N, P,. K, Ca, Mg, Na, Fe, Mn, Zn and Cu in citrus and pineapple leaves are presented. 7. It is shown that diurnal variations in nutrient concentrations occur in citrus and pineapple leaves. 8. The variations in N, P, K, Ca, Mg, Na, Fe, Mn, Zn and Cu, occurring from tree to tree in 3 different Navel orange blocks are presented. It is shown that if all these elements are to be represented . to within 10% of the mean values on a 19 : 1 probability level, all the trees in the blocks would have to be sampled. Reasonable sampling procedures for various purposes are suggested. 9. The variations in N, P, K, Ca, Mg, Fe, Mn, Zn and Cu, occurring in 3 different Cayenne pineapple plantations are presented and described. Suitable sampling procedures are suggested.
- Full Text:
- Date Issued: 1958
The spectrochemical determination of certain minor trace elements in plant material
- Authors: Eve, Desmond John
- Date: 1961
- Subjects: Trace elements Spectrum analysis Plants -- Analysis Plants -- Effect of trace elements on Trace elements in agriculture
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4469 , http://hdl.handle.net/10962/d1011773
- Description: A study has been made of three organic complexing reagents , namely dithizone, oxine and cupferron with a view to developing suitable methods for the separation and concentration of Zn, Co, Ni, Pb, Cu, Mn, Ti , V and Mo prior to the spectrometric determination of their concentrations. In particular the influence of pH on the chloroform extraction of ditihizonates, oxinates and cupferrates from aqueous tartrate and citrate solutions and the separation of iron by oxine extraction has been investigated. The development of a method for the chemical concentration and spectrcgraphic determination of Zn, Co, Ni, Pb, Ti, V and Mo is described and the possibility of determining Nn and Cu flame photometrically as part of the analysis scheme is demonstrated. A specially designed slide rule for the calculation of spectrographic results is described. A direct reading spectrometric method for the determination of Zn, Pb and Cu in plant material is presented. The analysis of plant ash for zinc using the 2138 . 6A spectrum line has been studied and a simple, rapid analysis method is described.
- Full Text:
- Date Issued: 1961
- Authors: Eve, Desmond John
- Date: 1961
- Subjects: Trace elements Spectrum analysis Plants -- Analysis Plants -- Effect of trace elements on Trace elements in agriculture
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4469 , http://hdl.handle.net/10962/d1011773
- Description: A study has been made of three organic complexing reagents , namely dithizone, oxine and cupferron with a view to developing suitable methods for the separation and concentration of Zn, Co, Ni, Pb, Cu, Mn, Ti , V and Mo prior to the spectrometric determination of their concentrations. In particular the influence of pH on the chloroform extraction of ditihizonates, oxinates and cupferrates from aqueous tartrate and citrate solutions and the separation of iron by oxine extraction has been investigated. The development of a method for the chemical concentration and spectrcgraphic determination of Zn, Co, Ni, Pb, Ti, V and Mo is described and the possibility of determining Nn and Cu flame photometrically as part of the analysis scheme is demonstrated. A specially designed slide rule for the calculation of spectrographic results is described. A direct reading spectrometric method for the determination of Zn, Pb and Cu in plant material is presented. The analysis of plant ash for zinc using the 2138 . 6A spectrum line has been studied and a simple, rapid analysis method is described.
- Full Text:
- Date Issued: 1961
A comparative study of the catechin components in the barks of wattle species related to Acacia Mernsii
- Authors: Maihs, Edwin Alfred
- Date: 1962
- Subjects: Wattles (Plants) Acacia mearnsii Acacia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4482 , http://hdl.handle.net/10962/d1012793
- Description: The distribution of flavonoid constituents in the barks of Acacia mearnsii De Wild.(black wattle) , A· decurens Willd. (green wattle), A. dealbata Link.(silver wattle) and A. pycnantha Benth.(golden wattle) has been studied. Bark extracts of the four wattle species have been fractionated into low molecular weight fractions containing mainly catechins and other low molecular weight constituents, and high molecular weight fractions containing the bulk of the polymerized tannins. The low molecular weight fractions have been further fractionated by "preparative paper chromatography". (-)-Robinetinidol, (-)-7:3': 4': 5'-tetrahydroxy flavan- 3-ol, a new naturally occurring catechin, (+)-catechin and (+)-gallocatechin have been isolated from the barks of A. mearnsii, A. dealbata and A. pycnantha. (-)-Epicatechin and (-)-epigallocatechin have been identified in the bark extracts of A. dealbata and A. pycnantha, but appeared to be absent in the barks of A. mearnsii and A. decurrens. (-)-Epicatechin has been isolated fron A. dealbata, and both (-}-epicatechin and (-)-epigallocatechin were isolated from A. pycnantha. (-)-Epicatechin gallate, (-)-epigallocatechin gallate and gallic acid were isolated from A. pycnantha only. These three constituents appeared to be absent in the barks of the three other wattle species. (-)-Epigallocatechin, (-)-epicatechin gallate and (-)-epigallocatechin gallate which were not available for direct comparison, were subsequently isolated from green tea where they are present as major phenolic constituents. A method for the quantitative estimation of polyphenolic substances on two dimensional paper chromatograms has been developed, and a photoelectric densitometer constructed. Two spray reagents, ammoniacal silver nitrate and bisdiazotised benzidine, were found to give straight line relationships of instrument deflection against log concentration for flavonoid substances. This estimation method for the first time supplied means for a detailed study of the concentration of catechin constituents in the bark extracts of A. mearnsii, A. decurrens, A. dealbata, A. pycnantha and of A. mearnsii x A. decurrens hybrids. The concentration of catechin constituents has been shown to vary considerably between species whereas variation within species was small. In the latter respect silver wattle is an exception. Taxonomic significance may possibly be attached to the distribution of catechin constituents in the bark of the four Acacia species. The concentration of (-)-robinetinidol, which appears to be the characteristic compound of these Acacias, progressively decreases in the sequence black-, black x green hybrid, green-, silver- and golden wattle, while the number of catechin constituents of the "phloroglucinol series" increases in the same sequence. It thus appears, that by the examination of their bark components, a differentiation between species of a subgenera may be possible. Two tannins, constituents D and B, which are related to the leuco-anthocyanidins (flavan-3:4-diols) have been found in the barks of the four wattle species. One of the two, constituent D, was isolated in a pure form from the barks of A. mearnsii and A. pycnantha. Constituent D was found to generate robinetinidin and an orange pigment, the structure of which has not yet been fully identified. Compound D and its acetyl- and methoxyl derivatives did not crystallize. From the results of alkaline-, acidic- and enzymatic degradations, colour reactions and light-absorption studies, combustion analysis of the compound and its derivatives and molecular weight estimations, constituent D is surmised to be a dimer of 7:3': 4': 5'-tetrahydroxyflavan-3:4-diol (leuco-robinetinidin), The isolation of this complex leuco-anthocyanidin tannin represents the first isolation of a flavonoid tannin from commercial vegetable tannin sources. The second tannin obtained from the bark of A.mearnsii, "constituent B" appears to consist of two overlapping substances, which have not yet been separated. The tannin (B) was found to have an average molecular weight of 676 and it is considered likely that both substances may be dimolecular. On heating with mineral acid robinetinidin, fisetinidin and an orange pigment are generated, the pigment being identical with the pigment generated from constituent D. It may therefore be assumed that "Constituent B" consists of a mixture of complex leuco-robinetinidins and leucofisetinidins. The distribution of complex leuco-anthocyanidins in the bark extracts of Acacia mearnsii, A. decurrens, A. dealbata and A. pycnantha has been examined. A correlation between the distribution of leuco-anthocyanidins in the bark of the four wattle species, and accepted systematics, does not, apparently, exist.
- Full Text:
- Date Issued: 1962
- Authors: Maihs, Edwin Alfred
- Date: 1962
- Subjects: Wattles (Plants) Acacia mearnsii Acacia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4482 , http://hdl.handle.net/10962/d1012793
- Description: The distribution of flavonoid constituents in the barks of Acacia mearnsii De Wild.(black wattle) , A· decurens Willd. (green wattle), A. dealbata Link.(silver wattle) and A. pycnantha Benth.(golden wattle) has been studied. Bark extracts of the four wattle species have been fractionated into low molecular weight fractions containing mainly catechins and other low molecular weight constituents, and high molecular weight fractions containing the bulk of the polymerized tannins. The low molecular weight fractions have been further fractionated by "preparative paper chromatography". (-)-Robinetinidol, (-)-7:3': 4': 5'-tetrahydroxy flavan- 3-ol, a new naturally occurring catechin, (+)-catechin and (+)-gallocatechin have been isolated from the barks of A. mearnsii, A. dealbata and A. pycnantha. (-)-Epicatechin and (-)-epigallocatechin have been identified in the bark extracts of A. dealbata and A. pycnantha, but appeared to be absent in the barks of A. mearnsii and A. decurrens. (-)-Epicatechin has been isolated fron A. dealbata, and both (-}-epicatechin and (-)-epigallocatechin were isolated from A. pycnantha. (-)-Epicatechin gallate, (-)-epigallocatechin gallate and gallic acid were isolated from A. pycnantha only. These three constituents appeared to be absent in the barks of the three other wattle species. (-)-Epigallocatechin, (-)-epicatechin gallate and (-)-epigallocatechin gallate which were not available for direct comparison, were subsequently isolated from green tea where they are present as major phenolic constituents. A method for the quantitative estimation of polyphenolic substances on two dimensional paper chromatograms has been developed, and a photoelectric densitometer constructed. Two spray reagents, ammoniacal silver nitrate and bisdiazotised benzidine, were found to give straight line relationships of instrument deflection against log concentration for flavonoid substances. This estimation method for the first time supplied means for a detailed study of the concentration of catechin constituents in the bark extracts of A. mearnsii, A. decurrens, A. dealbata, A. pycnantha and of A. mearnsii x A. decurrens hybrids. The concentration of catechin constituents has been shown to vary considerably between species whereas variation within species was small. In the latter respect silver wattle is an exception. Taxonomic significance may possibly be attached to the distribution of catechin constituents in the bark of the four Acacia species. The concentration of (-)-robinetinidol, which appears to be the characteristic compound of these Acacias, progressively decreases in the sequence black-, black x green hybrid, green-, silver- and golden wattle, while the number of catechin constituents of the "phloroglucinol series" increases in the same sequence. It thus appears, that by the examination of their bark components, a differentiation between species of a subgenera may be possible. Two tannins, constituents D and B, which are related to the leuco-anthocyanidins (flavan-3:4-diols) have been found in the barks of the four wattle species. One of the two, constituent D, was isolated in a pure form from the barks of A. mearnsii and A. pycnantha. Constituent D was found to generate robinetinidin and an orange pigment, the structure of which has not yet been fully identified. Compound D and its acetyl- and methoxyl derivatives did not crystallize. From the results of alkaline-, acidic- and enzymatic degradations, colour reactions and light-absorption studies, combustion analysis of the compound and its derivatives and molecular weight estimations, constituent D is surmised to be a dimer of 7:3': 4': 5'-tetrahydroxyflavan-3:4-diol (leuco-robinetinidin), The isolation of this complex leuco-anthocyanidin tannin represents the first isolation of a flavonoid tannin from commercial vegetable tannin sources. The second tannin obtained from the bark of A.mearnsii, "constituent B" appears to consist of two overlapping substances, which have not yet been separated. The tannin (B) was found to have an average molecular weight of 676 and it is considered likely that both substances may be dimolecular. On heating with mineral acid robinetinidin, fisetinidin and an orange pigment are generated, the pigment being identical with the pigment generated from constituent D. It may therefore be assumed that "Constituent B" consists of a mixture of complex leuco-robinetinidins and leucofisetinidins. The distribution of complex leuco-anthocyanidins in the bark extracts of Acacia mearnsii, A. decurrens, A. dealbata and A. pycnantha has been examined. A correlation between the distribution of leuco-anthocyanidins in the bark of the four wattle species, and accepted systematics, does not, apparently, exist.
- Full Text:
- Date Issued: 1962
Prototypes of black wattle tannins and their stereochemistry
- Authors: Drewes, Siegfried Ernst
- Date: 1963
- Subjects: Tannins -- Anthocyanidis Stereochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4460 , http://hdl.handle.net/10962/d1011437
- Description: A number of interrelated flavonoid compounds, present in trace quantities in mature black wattle (Acacia mearnsii De Wild) bark, have been isolated and identified for the first time. They include a) the resorcinol-pyrogallol analogues, (+)-leuco-robinetinidin (7,5',4',5'-tetrahydroxyflavan-3,4-diol), dihydrorobinetin (7,5',4',5'-tetrahydroxyflavan-3-ol-4-one) and robtein (2',4',5,4,5- pentahydroxychalcone) and b) the resorcinol-catechol analogues, (+)-leuco-fisetinidin (7,3',4'-trihydroxyflavan-3,4-diol), fustin (7,3',4'-trihydroxyflavan-3-ol-4-one), (-)-fisetinidol (7,3',4'trihydroxyflavan- 3-ol), butein (2',4',3,4-tetrahydroxychalcone) and butin (7,5',4'-trihydroxyflavan-4-one). In addition, two flavonol glycosides, myricitrin (3,5,7,3',4',5'-hexahydroxyflavone-3-rhamnoside ) and quercitrin (5,5,7,5',4'-pentahydroxyflavone-3-rhamnoside), which belong to the phloroglucinol-pyrogallol and phloroglucinolcatechol class of flavonoids respectively, were isolated from immature bark. These represent the only glycosides isolated hitherto from wattle bark or heartwood extracts. Summary, p. i.
- Full Text:
- Date Issued: 1963
- Authors: Drewes, Siegfried Ernst
- Date: 1963
- Subjects: Tannins -- Anthocyanidis Stereochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4460 , http://hdl.handle.net/10962/d1011437
- Description: A number of interrelated flavonoid compounds, present in trace quantities in mature black wattle (Acacia mearnsii De Wild) bark, have been isolated and identified for the first time. They include a) the resorcinol-pyrogallol analogues, (+)-leuco-robinetinidin (7,5',4',5'-tetrahydroxyflavan-3,4-diol), dihydrorobinetin (7,5',4',5'-tetrahydroxyflavan-3-ol-4-one) and robtein (2',4',5,4,5- pentahydroxychalcone) and b) the resorcinol-catechol analogues, (+)-leuco-fisetinidin (7,3',4'-trihydroxyflavan-3,4-diol), fustin (7,3',4'-trihydroxyflavan-3-ol-4-one), (-)-fisetinidol (7,3',4'trihydroxyflavan- 3-ol), butein (2',4',3,4-tetrahydroxychalcone) and butin (7,5',4'-trihydroxyflavan-4-one). In addition, two flavonol glycosides, myricitrin (3,5,7,3',4',5'-hexahydroxyflavone-3-rhamnoside ) and quercitrin (5,5,7,5',4'-pentahydroxyflavone-3-rhamnoside), which belong to the phloroglucinol-pyrogallol and phloroglucinolcatechol class of flavonoids respectively, were isolated from immature bark. These represent the only glycosides isolated hitherto from wattle bark or heartwood extracts. Summary, p. i.
- Full Text:
- Date Issued: 1963
A study of irradiation effects in solids
- Authors: Brown, Michael Ewart
- Date: 1966
- Subjects: Decomposition (Chemistry) , Crystals -- Thermal properties , Oxalates -- Thermal properties , Solids -- Effect of radiation on
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4509 , http://hdl.handle.net/10962/d1013387
- Description: One of the primary objects of this research was to determine, if possible, the nature of the radiation damage prior to thermal decomposition. The X-ray study has not wholly achieved this although more information has been derived from it than from similar work on AgMnO₄ However, the diffuse reflections obtained do indicate, quite strongly, the creation of point defects during irradiation. This is of value since such assumptions have been made in the explanation of the kinetics of decomposition of a number of irradiated solids (BaN₆,CaN₆). In addition the X-ray work has suggested future research which should produce useful information; namely, a precise study of the diffuse reflections. Another object of the research was to attempt to determine what characteristics, if any, of the kinetics of the decomposition of an unirradiated solid would predetermine a marked irradiation effect. It is obvious that the type of nuclear growth which occurs e.g. branching chain, or power law, does not characterise a substance with regard to a possible irradiation effect . The photosensitivity, or otherwise, also does not determine whether there will be an irradiation effect. However, the one property that the substances which have been studied, have in common, is a polyatomic anion, but here again ammonium dichromate does not show an acceleration of the decomposition after irradiation. Consequently it is considered that it is not possible to say, a priori, whether a solid will undergo an accelerated decomposition after irradiation. Each new solid, unless it belongs to a particular class e.g. the alkaline earth azides , must be considered afresh. Nevertheless it does appear that the irradiation effect can take two forms: - (i) the production of an unstable compound e.g. nickel oxalate, the decomposition of which affects the normal pyrolysis; and (ii) the production of point defects which determine the nature of the subsequent thermal decomposition e.g . CaN₆ . It is possible that the effect requires an interaction of the created point defects with the existing line defects.
- Full Text:
- Date Issued: 1966
- Authors: Brown, Michael Ewart
- Date: 1966
- Subjects: Decomposition (Chemistry) , Crystals -- Thermal properties , Oxalates -- Thermal properties , Solids -- Effect of radiation on
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4509 , http://hdl.handle.net/10962/d1013387
- Description: One of the primary objects of this research was to determine, if possible, the nature of the radiation damage prior to thermal decomposition. The X-ray study has not wholly achieved this although more information has been derived from it than from similar work on AgMnO₄ However, the diffuse reflections obtained do indicate, quite strongly, the creation of point defects during irradiation. This is of value since such assumptions have been made in the explanation of the kinetics of decomposition of a number of irradiated solids (BaN₆,CaN₆). In addition the X-ray work has suggested future research which should produce useful information; namely, a precise study of the diffuse reflections. Another object of the research was to attempt to determine what characteristics, if any, of the kinetics of the decomposition of an unirradiated solid would predetermine a marked irradiation effect. It is obvious that the type of nuclear growth which occurs e.g. branching chain, or power law, does not characterise a substance with regard to a possible irradiation effect . The photosensitivity, or otherwise, also does not determine whether there will be an irradiation effect. However, the one property that the substances which have been studied, have in common, is a polyatomic anion, but here again ammonium dichromate does not show an acceleration of the decomposition after irradiation. Consequently it is considered that it is not possible to say, a priori, whether a solid will undergo an accelerated decomposition after irradiation. Each new solid, unless it belongs to a particular class e.g. the alkaline earth azides , must be considered afresh. Nevertheless it does appear that the irradiation effect can take two forms: - (i) the production of an unstable compound e.g. nickel oxalate, the decomposition of which affects the normal pyrolysis; and (ii) the production of point defects which determine the nature of the subsequent thermal decomposition e.g . CaN₆ . It is possible that the effect requires an interaction of the created point defects with the existing line defects.
- Full Text:
- Date Issued: 1966
An examination of the extractives of Leonotis species
- Authors: Kaplan, Errol R
- Date: 1966
- Subjects: Leonotis -- Analysis Botanical chemistry Chemistry, Analytic Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4481 , http://hdl.handle.net/10962/d1012628
- Description: Marrubiin and the other two diterpenoids, compounds X and Y, which had previously been isolated from Leonotus leonurus have been reinvestigated. Although the structure for marrubiin is well known its stereochemistry has been the subject of protracted discussion and is by no means secure except at C₅ and C₁₀ . N.M.R. spectral evidence showed that the lactone ring was cis-fused and β-orientated. Dehydration experiments carried out by previous workers were repeated, in order to resolve the residual uncertainty regarding the stereochemistry at C₉, an attempt was made to prepare iodoacetyl marrubic acid for X-ray crystallographic studies. Compound Y, C₂₀H₂₈0₃, a triply-unsaturated compound was shown by spectral studies to contain a furan ring and an α,β- unsaturated keto-group. It possesses a hydroxyl group incapable of acetylation, but readily removed by alkali and dehydrating agents to yield a tetraunsaturated compound, anhydro~Y; the hydroxyl is thus tertiary, Isolation of 1:2:5-trimethylnaphthalene on dehydrogenation indicated a relationship with the labdane diterpene group and supported the C₂₀ formula, The position of the α,β-unsaturated keto-group was resolved by interpretation of the ultraviolet spectra of degradation products and also by isolation of 1:2:3:5- trimethylnaphthalene on dehydrogenation of a suitable grignard product, The presence of a β-substituted furan was further indicated by colour reactions and confirmed by mass and n.m.r. spectra. The skeleton of compound Y is correlated with marrubiin via "iso-ambreinolide " and its stereochemistry is discussed. Further stereochemical assignments are postulated from the study of the n.m.r. spectra. Compound X, C₂₀H₂₈0₅, was shown by spectral and chemical evidence to be a diterpenoid dilactone containing an ether bridge between C₉ and C₁₃ Isolation of 1:2:5 trimethylnaphthal ene on dehydrogenation showed it to be closely related to marrubiin, This was supported by n.m.r. spectral results. A structure for compound X is proposed and the stereochemistry discussed. The aerial portions of Leonotis leonitis were also extracted and shown to contain a new compound, compound R. Preliminary investigation showed that it was a dilactone containing a furan ring, The n.m.r. spectrum of the compound is discussed.
- Full Text:
- Date Issued: 1966
- Authors: Kaplan, Errol R
- Date: 1966
- Subjects: Leonotis -- Analysis Botanical chemistry Chemistry, Analytic Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4481 , http://hdl.handle.net/10962/d1012628
- Description: Marrubiin and the other two diterpenoids, compounds X and Y, which had previously been isolated from Leonotus leonurus have been reinvestigated. Although the structure for marrubiin is well known its stereochemistry has been the subject of protracted discussion and is by no means secure except at C₅ and C₁₀ . N.M.R. spectral evidence showed that the lactone ring was cis-fused and β-orientated. Dehydration experiments carried out by previous workers were repeated, in order to resolve the residual uncertainty regarding the stereochemistry at C₉, an attempt was made to prepare iodoacetyl marrubic acid for X-ray crystallographic studies. Compound Y, C₂₀H₂₈0₃, a triply-unsaturated compound was shown by spectral studies to contain a furan ring and an α,β- unsaturated keto-group. It possesses a hydroxyl group incapable of acetylation, but readily removed by alkali and dehydrating agents to yield a tetraunsaturated compound, anhydro~Y; the hydroxyl is thus tertiary, Isolation of 1:2:5-trimethylnaphthalene on dehydrogenation indicated a relationship with the labdane diterpene group and supported the C₂₀ formula, The position of the α,β-unsaturated keto-group was resolved by interpretation of the ultraviolet spectra of degradation products and also by isolation of 1:2:3:5- trimethylnaphthalene on dehydrogenation of a suitable grignard product, The presence of a β-substituted furan was further indicated by colour reactions and confirmed by mass and n.m.r. spectra. The skeleton of compound Y is correlated with marrubiin via "iso-ambreinolide " and its stereochemistry is discussed. Further stereochemical assignments are postulated from the study of the n.m.r. spectra. Compound X, C₂₀H₂₈0₅, was shown by spectral and chemical evidence to be a diterpenoid dilactone containing an ether bridge between C₉ and C₁₃ Isolation of 1:2:5 trimethylnaphthal ene on dehydrogenation showed it to be closely related to marrubiin, This was supported by n.m.r. spectral results. A structure for compound X is proposed and the stereochemistry discussed. The aerial portions of Leonotis leonitis were also extracted and shown to contain a new compound, compound R. Preliminary investigation showed that it was a dilactone containing a furan ring, The n.m.r. spectrum of the compound is discussed.
- Full Text:
- Date Issued: 1966
The thermal decomposition of mercuric oxalate and inorganic azides
- Authors: Moore, D J
- Date: 1966
- Subjects: Decomposition (Chemistry) , Oxalates -- Thermal properties , Mercuric Oxide -- Azides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4483 , http://hdl.handle.net/10962/d1012878
- Description: The chemical reactivity of a solid is influenced to a marked degree by the presence of imperfections or defects in the solid. Bond strengths are considerably weaker at points of imperfection than elsewhere in the solid, and hence the initiation of reaction is favoured at these sites due to the relative ease of bond rupture. Line defects, such as edge or screw dislocations, jogs, Smekul cracks etc, are of prime importance in such changes. The surface of a solid or in intergranular boundaries, where a state of strain exists, are also favourable places for the initiation of a reaction, Point defects e.g. vacancies or interstitialions or atoms also play important roles in chemical change, often in conjuction with line defects.
- Full Text:
- Date Issued: 1966
- Authors: Moore, D J
- Date: 1966
- Subjects: Decomposition (Chemistry) , Oxalates -- Thermal properties , Mercuric Oxide -- Azides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4483 , http://hdl.handle.net/10962/d1012878
- Description: The chemical reactivity of a solid is influenced to a marked degree by the presence of imperfections or defects in the solid. Bond strengths are considerably weaker at points of imperfection than elsewhere in the solid, and hence the initiation of reaction is favoured at these sites due to the relative ease of bond rupture. Line defects, such as edge or screw dislocations, jogs, Smekul cracks etc, are of prime importance in such changes. The surface of a solid or in intergranular boundaries, where a state of strain exists, are also favourable places for the initiation of a reaction, Point defects e.g. vacancies or interstitialions or atoms also play important roles in chemical change, often in conjuction with line defects.
- Full Text:
- Date Issued: 1966
Synthesis of flavan-3, 4-diols, stereochemistry of novel biflavanols and new non-tannins from Acacia Mearnsii
- Authors: Saayman, Henry Martin
- Date: 1967
- Subjects: Tannins Acacia mearnsii Stereochemistry Wattles (Plants) Chemistry, Analytic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4444 , http://hdl.handle.net/10962/d1007704
- Description: From Summary: The structural elucidation of condensed tannins, which are considered to consist of C₁₅-flavan units, presents certain difficulties. These tannins occur in extremely complex mixtures, and their isolation is complicated by their susceptibility to oxidative denaturation. Limitations in the formation of significant degradation products add to these problems. Since condensed tannins of black wattle bark yield anthocyanidins on treatment with mineral acids, they are considered to be proanthocyanidin in character. For this reason the initial approach to the investigation of the structures of condensed tannins was by way of the synthesis of novel 7-hydroxyflavan-3,4-diols having a low degree of hydroxyl substitution. Submission of these to modern physical techniques such as nuclear magnetic resonance (n.m.r.) spectroscopy would yield valuable data regarding the chemical shifts and coupling constants of heterocyclic and benzenoid protons which may be used for subsequent work on more highly hydroxylated diols, biflavanols and finally the condensed tannins themselves.
- Full Text:
- Date Issued: 1967
- Authors: Saayman, Henry Martin
- Date: 1967
- Subjects: Tannins Acacia mearnsii Stereochemistry Wattles (Plants) Chemistry, Analytic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4444 , http://hdl.handle.net/10962/d1007704
- Description: From Summary: The structural elucidation of condensed tannins, which are considered to consist of C₁₅-flavan units, presents certain difficulties. These tannins occur in extremely complex mixtures, and their isolation is complicated by their susceptibility to oxidative denaturation. Limitations in the formation of significant degradation products add to these problems. Since condensed tannins of black wattle bark yield anthocyanidins on treatment with mineral acids, they are considered to be proanthocyanidin in character. For this reason the initial approach to the investigation of the structures of condensed tannins was by way of the synthesis of novel 7-hydroxyflavan-3,4-diols having a low degree of hydroxyl substitution. Submission of these to modern physical techniques such as nuclear magnetic resonance (n.m.r.) spectroscopy would yield valuable data regarding the chemical shifts and coupling constants of heterocyclic and benzenoid protons which may be used for subsequent work on more highly hydroxylated diols, biflavanols and finally the condensed tannins themselves.
- Full Text:
- Date Issued: 1967
The effect of ultraviolet and gamma irradation on soluble calf-skin collagen
- Authors: Davidson, Raymond John
- Date: 1967
- Subjects: Collagen -- Hide powder Irradiation Solids -- Effect of radiation on Gamma rays -- Dose-response relationship
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4290 , http://hdl.handle.net/10962/d1003718
- Description: Initially the present study was confined to the effects of ultraviolet irradiation on acid-soluble collagen. Such a study was undertaken in order to demonstrate the critical role played by tyrosine and phenylalanine in the intermolecular interaction of the telopeptides protruding from the rigid parent collagen molecule. Since both tyrosine and phenylalanine are photosensitive, and because the collagen telopeptides are relatively rich in these aromatic amino acids, carefully controlled degradation studies involving telopeptide liberation could be made. It became increasingly apparent during the course of investigation, that a better understanding of the subunit composition of thermally denatured acid-soluble collagen was necessary if a satisfactory interpretation of the irradiation studies was to be made. A subsequent study of the subunit composition of thermally denatured acid-soluble collagen resulted in the isolation and characterisation of two major and two minor dimeric components as well as the α- and β - subunits. Three acidic telopeptides and three basic telopeptides were also isolated from acid-soluble collagen during the course of the present study. The presence of the dimeric components while related directly to the method of preparation, suggested that acid-soluble collagen was largely dimeric in nature. Such a conclusion suggested an intermolecular rather than an intraolecular relationship between neutral-salt-soluble and acid-soluble collagen. While it is currently accepted that an intramolecular relationship exists between neutral-salt-soluble and acid-soluble collagen, such a relationship does not satisfactorily explain the very different solubility characteristics displayed by these soluble collagen extracts. With this in mind, and using the study on the subunit composition of thermally denatured acid-soluble collagen as a basis for comparison, the intra and intermolecular relationship between neutral-salt-soluble and acid-soluble collagen was investigated using ultraviolet and gamma irradiation. The effects of ultraviolet and gamma irradiation on soluble collagen preparations proved very similar. Although collagen samples were irradiated in solution from an ultraviolet source; and under anhydrous conditions from a gamma source, much the same degradation mechanism resulted. The initial depolymerisation of dimeric material followed by peptide fission, yielding irradiation-resistant crystalline portions of the parent triple helix, took place in both instances. At the same time, both studies indicated no significant differences in the intra or intermolecular structures of the neutral-salt-soluble and acid-soluble preparations investigated. The dimer content of neutral-salt-soluble collagen preparations was, however, noted to be smaller. To current methods for the preparation of soluble collagens, it may be concluded that such preparations are peptideless to some degree. While the native tropocollagen monomer with its full complement of telopeptide side chains may actively undergo linear polymerisation resulting in fibre formation, the soluble collagen preparations referred to above may only aggregate in a rather random fashion.
- Full Text:
- Date Issued: 1967
- Authors: Davidson, Raymond John
- Date: 1967
- Subjects: Collagen -- Hide powder Irradiation Solids -- Effect of radiation on Gamma rays -- Dose-response relationship
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4290 , http://hdl.handle.net/10962/d1003718
- Description: Initially the present study was confined to the effects of ultraviolet irradiation on acid-soluble collagen. Such a study was undertaken in order to demonstrate the critical role played by tyrosine and phenylalanine in the intermolecular interaction of the telopeptides protruding from the rigid parent collagen molecule. Since both tyrosine and phenylalanine are photosensitive, and because the collagen telopeptides are relatively rich in these aromatic amino acids, carefully controlled degradation studies involving telopeptide liberation could be made. It became increasingly apparent during the course of investigation, that a better understanding of the subunit composition of thermally denatured acid-soluble collagen was necessary if a satisfactory interpretation of the irradiation studies was to be made. A subsequent study of the subunit composition of thermally denatured acid-soluble collagen resulted in the isolation and characterisation of two major and two minor dimeric components as well as the α- and β - subunits. Three acidic telopeptides and three basic telopeptides were also isolated from acid-soluble collagen during the course of the present study. The presence of the dimeric components while related directly to the method of preparation, suggested that acid-soluble collagen was largely dimeric in nature. Such a conclusion suggested an intermolecular rather than an intraolecular relationship between neutral-salt-soluble and acid-soluble collagen. While it is currently accepted that an intramolecular relationship exists between neutral-salt-soluble and acid-soluble collagen, such a relationship does not satisfactorily explain the very different solubility characteristics displayed by these soluble collagen extracts. With this in mind, and using the study on the subunit composition of thermally denatured acid-soluble collagen as a basis for comparison, the intra and intermolecular relationship between neutral-salt-soluble and acid-soluble collagen was investigated using ultraviolet and gamma irradiation. The effects of ultraviolet and gamma irradiation on soluble collagen preparations proved very similar. Although collagen samples were irradiated in solution from an ultraviolet source; and under anhydrous conditions from a gamma source, much the same degradation mechanism resulted. The initial depolymerisation of dimeric material followed by peptide fission, yielding irradiation-resistant crystalline portions of the parent triple helix, took place in both instances. At the same time, both studies indicated no significant differences in the intra or intermolecular structures of the neutral-salt-soluble and acid-soluble preparations investigated. The dimer content of neutral-salt-soluble collagen preparations was, however, noted to be smaller. To current methods for the preparation of soluble collagens, it may be concluded that such preparations are peptideless to some degree. While the native tropocollagen monomer with its full complement of telopeptide side chains may actively undergo linear polymerisation resulting in fibre formation, the soluble collagen preparations referred to above may only aggregate in a rather random fashion.
- Full Text:
- Date Issued: 1967
A structural investigation of the sulphated polysaccharides of Aeodes orbitosa and Phyllymenia cornea
- Authors: Parolis, Haralambos
- Date: 1968
- Subjects: Polysaccharides , Marine algae -- Composition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4487 , http://hdl.handle.net/10962/d1012999
- Description: A highly sulphated, methylated polysaccharide, aeodan, isolated from the red seaweed Aeodes orbitosa was shown to contain galactose, 2-̲̲O-methyl-D-galactose, 4-O̲-methyl-Lgalactose, 6-O̲-methyl-D-galactose, xylose, and glycerol. The polysaccharide was desulphated with methanolic hydrogen chloride. Periodate oxidation of aeodan and desulphated aeodan, followed by reduction and hydrolysis, revealed the presence of 1,4- and 1,3-linked galactose residues and 1,3-linked 6-O̲-methy l-D-galactose residues in aeodan. Treatment of aeodan with sodium hydroxide revealed that the majority of the ester sulphate groups were alkali stable. Methylation of desulphated aeodan revealed that the polysaccharide was composed entirely of 1,3 and 1,4 links. Methylation of aeodan revealed the presence of 1,3- and 1,4- linked units, 1,3-linked galactose-2-sulphate, and 1,3-linked galactose-2, 6-disulphate units in the polysaccharide. Partial hydrolysis of aeodan resulted in the isolation and characterisation of 3-O̲-D-galactopyranosyl-D-galactose and 4-O̲-ß-D-galactopyranosyl- D-galactose. A sulphated, methylated polysaccharide, phyllymenan, isolated from the red seaweed Phyllymenia cornea was shown to contain galactose, 2-O̲-methyl-D-galactose, 4-O̲-methyl L- galactose , 6-O̲-methyl -D-galactose, and xylose. The polysaccharide was completely desulphated with methanolic hydrogen chloride. Periodate oxidation of phyllymenan before and after desulphation revealed that removal of the sulphate ester groups had not produced any new adjacent hydroxyl groups. Alkali treatment of phyllymenan revealed that the ester sulphate groups were alkali stable. Methylation studies on phyllymenan revealed the presence of 1,3- and 1,4-linked units, 1,3-linked galactose-2-sulphate, and 1,3-linked galactose- 2,6-disulphate units in the polysaccharide. Partial hydrolysis of phyllymenan revealed the presence or 4-O-̲ß- D-Dgalactopyranosyl- D-galactosc, 4-O-̲ß-D-galactopyranosyl -2-0- methyl-D-galactose, a galactosylgalactose composed of D and L-galactose, and adjacent 6-O̲-methyl- and 2-O̲-methyl-D- galactose units in the polysaccharide.
- Full Text:
- Date Issued: 1968
- Authors: Parolis, Haralambos
- Date: 1968
- Subjects: Polysaccharides , Marine algae -- Composition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4487 , http://hdl.handle.net/10962/d1012999
- Description: A highly sulphated, methylated polysaccharide, aeodan, isolated from the red seaweed Aeodes orbitosa was shown to contain galactose, 2-̲̲O-methyl-D-galactose, 4-O̲-methyl-Lgalactose, 6-O̲-methyl-D-galactose, xylose, and glycerol. The polysaccharide was desulphated with methanolic hydrogen chloride. Periodate oxidation of aeodan and desulphated aeodan, followed by reduction and hydrolysis, revealed the presence of 1,4- and 1,3-linked galactose residues and 1,3-linked 6-O̲-methy l-D-galactose residues in aeodan. Treatment of aeodan with sodium hydroxide revealed that the majority of the ester sulphate groups were alkali stable. Methylation of desulphated aeodan revealed that the polysaccharide was composed entirely of 1,3 and 1,4 links. Methylation of aeodan revealed the presence of 1,3- and 1,4- linked units, 1,3-linked galactose-2-sulphate, and 1,3-linked galactose-2, 6-disulphate units in the polysaccharide. Partial hydrolysis of aeodan resulted in the isolation and characterisation of 3-O̲-D-galactopyranosyl-D-galactose and 4-O̲-ß-D-galactopyranosyl- D-galactose. A sulphated, methylated polysaccharide, phyllymenan, isolated from the red seaweed Phyllymenia cornea was shown to contain galactose, 2-O̲-methyl-D-galactose, 4-O̲-methyl L- galactose , 6-O̲-methyl -D-galactose, and xylose. The polysaccharide was completely desulphated with methanolic hydrogen chloride. Periodate oxidation of phyllymenan before and after desulphation revealed that removal of the sulphate ester groups had not produced any new adjacent hydroxyl groups. Alkali treatment of phyllymenan revealed that the ester sulphate groups were alkali stable. Methylation studies on phyllymenan revealed the presence of 1,3- and 1,4-linked units, 1,3-linked galactose-2-sulphate, and 1,3-linked galactose- 2,6-disulphate units in the polysaccharide. Partial hydrolysis of phyllymenan revealed the presence or 4-O-̲ß- D-Dgalactopyranosyl- D-galactosc, 4-O-̲ß-D-galactopyranosyl -2-0- methyl-D-galactose, a galactosylgalactose composed of D and L-galactose, and adjacent 6-O̲-methyl- and 2-O̲-methyl-D- galactose units in the polysaccharide.
- Full Text:
- Date Issued: 1968
The growth of flue-cured tobacco in acid soils
- Authors: Ryding, William Wallace
- Date: 1969
- Subjects: Flue-cured tobacco -- Zimbabwe , Acid soils -- Zimbabwe
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4495 , http://hdl.handle.net/10962/d1013110
- Description: The main effects of lime, aluminium, iron and manganese were studied in field and greenhouse grown tobacco; relations between soil and plant measurements were examined. Ground limestone, ground mixed lime, ground dolomite and slaked lime at rates equivalent to 1,000 and 2,000 lb. CaC0₃/acre increased yield and quality of flue-cured tobacco both on Triassic and granite sands, whether applied early (February/March) or late (September); the highest rate and late application were often best. Yields increased with 4,000 and 6,000 lb. dolomite/acre applied late, but quality decreased when the pH was about 6.0. Lime did not affect leaf maturity as reflected by nitrogen and reducing sugars concentration . Where leaf discolouration (slate) occurred, the best quality and least discoloured leaf had the lowest manganese concentration and was grown on limed soil. On a very acid and probably nitrogen deficient soil, lime, borax and nitrogen (nitrate only tested) reduced the discolouration and improved the quality, but potassium sulphate increased discolouration and decreased quality. Calcium concentration in the leaf was increased by lime, particularly calcitic materials, and magnesium concentration was increased by dolomite. Lime also increased the filling value and petroleum ether extract, but decreased manganese, boron, chloride and sometimes potassium, and had no effect on phosphorus, nitrogen, aluminium, iron, crude fibre, nicotine, reducing sugars and equilibrium moisture. The inorganic composition of greenhouse plants was similar; generally gypsum increased calcium concentration more than calcium carbonate but it did not affect manganese concentration, which was decreased by calcium carbonate. In the stem and roots of field grown plants (dolomite only tested), the concentration of magnesium was increased but the concentrations of calcium, potassium, aluminium and iron were unaffected. Although the concentration of nitrogen was increased and that of phosphorus was decreased in the stem, these were unaffected in the roots. Aluminium and iron behaved differently to other nutrient ions, being more concentrated in the roots than aerial plant parts. Boron and magnesium deficiencies were observed in a dry and wet year, respectively, suggesting that variable mineral deficiencies can affect responses to lime. Initially soil pH was affected more by source of lime, but later mostly by rates. Slaked lime increased the soil pH more than did ground limestone, mixed lime or dolomite. In a glasshouse experiment, pH was more important than calcium supply and in the field, the largest yields were often associated with the highest pH. In pot experiments, aluminium drastically reduced yields in nutrient solution but not in soils, whereas iron was more severe in soils; manganese had little effect on yield. Manganese was readily taken up and translocated to the tops, but aluminium and iron were mainly concentrated in the roots, as was found in field grown plants. Iron decreased manganese concentration in all plant parts and aluminium decreased calcium and manganese in nutrient solution only. Although aluminium and iron generally increased the concentration of phosphorus in the roots, they did not interfere with phosphorus transport in the plant. Manganese caused the leaf to become chlorotic and when no iron was present the upper leaves became yellow, and developed brown and white lesions. However, in soil grown plants, sufficient iron was present in the soil solution to prevent break down of tissue. Yellowing of the upper leaves also occurred when plants were grown in nutrient solution with aluminium and no iron; when both were present, the plants were darker in colour. Although aluminium damaged roots in nutrient solution, high rates of iron severely damaged leaves of plants grown in soil. Since the concentrations of aluminium, iron and manganese were decreased in the soil solution by liming, they were compared with plant growth and composition in 17 different soils, with and without lime. As was expected, lime increased soil pH. It also increased exchangeable calcium, but decreased exchangeable aluminium, iron and manganese; exchangeable magnesium and potassium and resin extractable phosphorus were not affected. As the Ratio Law does not hold for all Rhodesian soils, anion adsorption will be avoided if the soils are equilibrated with O.OOOSM CaC1₂; the concentrations of the cations in solution were affected in the same way as exchangeable cations, but phosphorus was increased. There was no relationship between yield of tobacco and its chemical composition. The correlations between soil solution data and plant composition were poor, except for manganese and phosphorus; the relation between Mn ppm. in plant vsa (superscript)Mn/a (superscript)Ca + Mg (enclosed in square root sign √) in solution, and P% vs pH₂ P0₄ or pH₂ P0₄ +½ pCa, were both curvilinear. On the other hand, all measurements of exchangeable cations were poorly correlated with plant composition. Finally yield was poorly correlated with soil solution data, and pH was as satisfactory as any other measurement tested. Manganese toxicity was observed on three soils, and a probable manganese deficiency on one. It was not possible to define a limit above which manganese toxicity occurred, but manganese deficiency developed at about 63 ppm. manganese. Variations in pH and the availability of aluminium, iron and manganese occurred when soils were incubated at about field capacity, generally the main effects having developed within seven days. In all soils, there was an initial increase in soil pH and a maximum value was reached in one to four days, decreasing by variable amounts with longer periods of incubation. Although the concentration of aluminium was larger than that of iron, the relation between both ions and soil pH was curvilinear, their concentrations increasing with decreasing pH. Increased temperature of incubation increased pH with a resultant decrease in the concentration of aluminium, but in one soil it appreciably increased the availability of iron in the early periods of incubation. Autumn and spring ploughing did not affect subsequent pH or the concentration of aluminium and iron in the soil solution. Manganese concentration varied from soil to soil and was not related to soil pH. In most soils there was a decrease in manganese concentration with length of incubation and it decreased more rapidly the lower the initial concentration. Temperature effects were variable and moisture affected the behaviour of manganese more than temperature. These findings and the distribution of aluminium, iron and manganese in the plant helped to explain the poor correlations.
- Full Text:
- Date Issued: 1969
- Authors: Ryding, William Wallace
- Date: 1969
- Subjects: Flue-cured tobacco -- Zimbabwe , Acid soils -- Zimbabwe
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4495 , http://hdl.handle.net/10962/d1013110
- Description: The main effects of lime, aluminium, iron and manganese were studied in field and greenhouse grown tobacco; relations between soil and plant measurements were examined. Ground limestone, ground mixed lime, ground dolomite and slaked lime at rates equivalent to 1,000 and 2,000 lb. CaC0₃/acre increased yield and quality of flue-cured tobacco both on Triassic and granite sands, whether applied early (February/March) or late (September); the highest rate and late application were often best. Yields increased with 4,000 and 6,000 lb. dolomite/acre applied late, but quality decreased when the pH was about 6.0. Lime did not affect leaf maturity as reflected by nitrogen and reducing sugars concentration . Where leaf discolouration (slate) occurred, the best quality and least discoloured leaf had the lowest manganese concentration and was grown on limed soil. On a very acid and probably nitrogen deficient soil, lime, borax and nitrogen (nitrate only tested) reduced the discolouration and improved the quality, but potassium sulphate increased discolouration and decreased quality. Calcium concentration in the leaf was increased by lime, particularly calcitic materials, and magnesium concentration was increased by dolomite. Lime also increased the filling value and petroleum ether extract, but decreased manganese, boron, chloride and sometimes potassium, and had no effect on phosphorus, nitrogen, aluminium, iron, crude fibre, nicotine, reducing sugars and equilibrium moisture. The inorganic composition of greenhouse plants was similar; generally gypsum increased calcium concentration more than calcium carbonate but it did not affect manganese concentration, which was decreased by calcium carbonate. In the stem and roots of field grown plants (dolomite only tested), the concentration of magnesium was increased but the concentrations of calcium, potassium, aluminium and iron were unaffected. Although the concentration of nitrogen was increased and that of phosphorus was decreased in the stem, these were unaffected in the roots. Aluminium and iron behaved differently to other nutrient ions, being more concentrated in the roots than aerial plant parts. Boron and magnesium deficiencies were observed in a dry and wet year, respectively, suggesting that variable mineral deficiencies can affect responses to lime. Initially soil pH was affected more by source of lime, but later mostly by rates. Slaked lime increased the soil pH more than did ground limestone, mixed lime or dolomite. In a glasshouse experiment, pH was more important than calcium supply and in the field, the largest yields were often associated with the highest pH. In pot experiments, aluminium drastically reduced yields in nutrient solution but not in soils, whereas iron was more severe in soils; manganese had little effect on yield. Manganese was readily taken up and translocated to the tops, but aluminium and iron were mainly concentrated in the roots, as was found in field grown plants. Iron decreased manganese concentration in all plant parts and aluminium decreased calcium and manganese in nutrient solution only. Although aluminium and iron generally increased the concentration of phosphorus in the roots, they did not interfere with phosphorus transport in the plant. Manganese caused the leaf to become chlorotic and when no iron was present the upper leaves became yellow, and developed brown and white lesions. However, in soil grown plants, sufficient iron was present in the soil solution to prevent break down of tissue. Yellowing of the upper leaves also occurred when plants were grown in nutrient solution with aluminium and no iron; when both were present, the plants were darker in colour. Although aluminium damaged roots in nutrient solution, high rates of iron severely damaged leaves of plants grown in soil. Since the concentrations of aluminium, iron and manganese were decreased in the soil solution by liming, they were compared with plant growth and composition in 17 different soils, with and without lime. As was expected, lime increased soil pH. It also increased exchangeable calcium, but decreased exchangeable aluminium, iron and manganese; exchangeable magnesium and potassium and resin extractable phosphorus were not affected. As the Ratio Law does not hold for all Rhodesian soils, anion adsorption will be avoided if the soils are equilibrated with O.OOOSM CaC1₂; the concentrations of the cations in solution were affected in the same way as exchangeable cations, but phosphorus was increased. There was no relationship between yield of tobacco and its chemical composition. The correlations between soil solution data and plant composition were poor, except for manganese and phosphorus; the relation between Mn ppm. in plant vsa (superscript)Mn/a (superscript)Ca + Mg (enclosed in square root sign √) in solution, and P% vs pH₂ P0₄ or pH₂ P0₄ +½ pCa, were both curvilinear. On the other hand, all measurements of exchangeable cations were poorly correlated with plant composition. Finally yield was poorly correlated with soil solution data, and pH was as satisfactory as any other measurement tested. Manganese toxicity was observed on three soils, and a probable manganese deficiency on one. It was not possible to define a limit above which manganese toxicity occurred, but manganese deficiency developed at about 63 ppm. manganese. Variations in pH and the availability of aluminium, iron and manganese occurred when soils were incubated at about field capacity, generally the main effects having developed within seven days. In all soils, there was an initial increase in soil pH and a maximum value was reached in one to four days, decreasing by variable amounts with longer periods of incubation. Although the concentration of aluminium was larger than that of iron, the relation between both ions and soil pH was curvilinear, their concentrations increasing with decreasing pH. Increased temperature of incubation increased pH with a resultant decrease in the concentration of aluminium, but in one soil it appreciably increased the availability of iron in the early periods of incubation. Autumn and spring ploughing did not affect subsequent pH or the concentration of aluminium and iron in the soil solution. Manganese concentration varied from soil to soil and was not related to soil pH. In most soils there was a decrease in manganese concentration with length of incubation and it decreased more rapidly the lower the initial concentration. Temperature effects were variable and moisture affected the behaviour of manganese more than temperature. These findings and the distribution of aluminium, iron and manganese in the plant helped to explain the poor correlations.
- Full Text:
- Date Issued: 1969
Theoretical aspects of the reaction of zirconium compunds and vegetable tannins with the chromium-collagen complex
- Williams-Wynn, David Ernest Arthur
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1969
- Subjects: Zirconium compounds , Collagen , Chromium compounds , Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4512 , http://hdl.handle.net/10962/d1013455
- Description: Studies have been made of the reactions which take place when zirconium compounds and vegetable tannins react with chromium tanned leather, in order to elucidate the mechanisms of the reactions which occur on retannage. Statistical procedures have been used in all investigations because of the variable nature of the substrate, and computer techniques have been applied to the repetitive statistical computations. Although chromium and vegetable tannages are well understood, further information on the reaction of zirconium with collagen was necessary before attempting to interpret the results of the studies of combination tannages with chromium, and this has been obtained by a comparative study of the reactions of chromium and zirconium with modified collagen. It is concluded that the mechanism of the reaction of basic zirconium sulphate with collagen is multipoint attachment of the tanning material by residual valency forces, although charge effects with basic groups may be supplementary. Zirconyl chloride reacts with carboxyl groups but does not form satisfactory, stable cross-links with collagen. Further evidence for this theory was obtained from the investigation of the reaction of zirconium compounds with chromium tanned collagen. Zirconyl sulphate does not interfere with effective chromium tannage and therefore can have little affinity for the carboxyl groups on the protein, but it displaces chromium complexes loosely held by auxiliary valencies without reducing the shrinkage temperature of the chromium leather Zirconyl chloride, although only fixed to a limited extent, apparently forms co-ordination compounds with the carboxyl groups, disrupting the chromium tannage because there is an over-all loss of hydrothermal stability. There is no evidence that zirconium co-ordinates with, or releases acid from chromium-collagen complexes, since combination chromium/zirconium tanned leathers are stable on storage. Retannage of chromium tanned leather with vegetable tanning materials generally results in loss of strength and a product which tends to deteriorate on ageing. Lower initial strength is probably due to the increased avidity of chromium tanned pelt for vegetable tannins, resulting from the liberation of internally neutralised reactive sites which are not normally available in vegetable tannage, and from the co- ordination of vegetable tannins and non-tannins to the chromium complex with the displacement of sulphate radicals. From a study of the retannage of chromium tanned modified collagen, it appears that basic groups probably play an important part in the rapid absorption of vegetable tannin. These reactions result in overloading of the fibre and an increased number of cross-links, both of which tend to produce weak leather. Deterioration with age is primarily a hydrolytic degradation of the protein which is catalysed by acid liberated from the chromium complexes by the entry of vegetable tannins, those factors which favour the formation of acid causing greater and more rapid deterioration.
- Full Text:
- Date Issued: 1969
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1969
- Subjects: Zirconium compounds , Collagen , Chromium compounds , Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4512 , http://hdl.handle.net/10962/d1013455
- Description: Studies have been made of the reactions which take place when zirconium compounds and vegetable tannins react with chromium tanned leather, in order to elucidate the mechanisms of the reactions which occur on retannage. Statistical procedures have been used in all investigations because of the variable nature of the substrate, and computer techniques have been applied to the repetitive statistical computations. Although chromium and vegetable tannages are well understood, further information on the reaction of zirconium with collagen was necessary before attempting to interpret the results of the studies of combination tannages with chromium, and this has been obtained by a comparative study of the reactions of chromium and zirconium with modified collagen. It is concluded that the mechanism of the reaction of basic zirconium sulphate with collagen is multipoint attachment of the tanning material by residual valency forces, although charge effects with basic groups may be supplementary. Zirconyl chloride reacts with carboxyl groups but does not form satisfactory, stable cross-links with collagen. Further evidence for this theory was obtained from the investigation of the reaction of zirconium compounds with chromium tanned collagen. Zirconyl sulphate does not interfere with effective chromium tannage and therefore can have little affinity for the carboxyl groups on the protein, but it displaces chromium complexes loosely held by auxiliary valencies without reducing the shrinkage temperature of the chromium leather Zirconyl chloride, although only fixed to a limited extent, apparently forms co-ordination compounds with the carboxyl groups, disrupting the chromium tannage because there is an over-all loss of hydrothermal stability. There is no evidence that zirconium co-ordinates with, or releases acid from chromium-collagen complexes, since combination chromium/zirconium tanned leathers are stable on storage. Retannage of chromium tanned leather with vegetable tanning materials generally results in loss of strength and a product which tends to deteriorate on ageing. Lower initial strength is probably due to the increased avidity of chromium tanned pelt for vegetable tannins, resulting from the liberation of internally neutralised reactive sites which are not normally available in vegetable tannage, and from the co- ordination of vegetable tannins and non-tannins to the chromium complex with the displacement of sulphate radicals. From a study of the retannage of chromium tanned modified collagen, it appears that basic groups probably play an important part in the rapid absorption of vegetable tannin. These reactions result in overloading of the fibre and an increased number of cross-links, both of which tend to produce weak leather. Deterioration with age is primarily a hydrolytic degradation of the protein which is catalysed by acid liberated from the chromium complexes by the entry of vegetable tannins, those factors which favour the formation of acid causing greater and more rapid deterioration.
- Full Text:
- Date Issued: 1969
Extractives of Leonotis and Euryops species
- Authors: Eagle, G A
- Date: 1971
- Subjects: Stereochemistry Leonotis -- Analysis Euryops -- Analysis Botanical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4465 , http://hdl.handle.net/10962/d1011610
- Description: The isolation and structure determination of dubiin and leonitin, two new diterpenoid acetates from Leonotis dubia and Leonotis leonitis respectively, are discussed. The compounds are diterpenoids of the labdane type and are closely related to marrubiin. The proposed structures are based on chemical and spectral evidence. Dubiin, C₂₂H₃₀0₆̕ contains a tertiary hydroxy- group, a furan ring and a ó-lactone while leonitin, C₂₂H₃₀0₇̕ is a γ - dilactone. at C-20. Both compounds are unusual in being oxygenated The extraction of three Euryops species and the isolation of euryopsol, C₂₂H₃₀0₄̕̕ are also described. A furanoeremophilane structure containing three hydroxy- groups, one of which is at a bridgehead position, is proposed. Euryopsol is the first furanoeremophilanoid with a substituent attached at C-IO
- Full Text:
- Date Issued: 1971
- Authors: Eagle, G A
- Date: 1971
- Subjects: Stereochemistry Leonotis -- Analysis Euryops -- Analysis Botanical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4465 , http://hdl.handle.net/10962/d1011610
- Description: The isolation and structure determination of dubiin and leonitin, two new diterpenoid acetates from Leonotis dubia and Leonotis leonitis respectively, are discussed. The compounds are diterpenoids of the labdane type and are closely related to marrubiin. The proposed structures are based on chemical and spectral evidence. Dubiin, C₂₂H₃₀0₆̕ contains a tertiary hydroxy- group, a furan ring and a ó-lactone while leonitin, C₂₂H₃₀0₇̕ is a γ - dilactone. at C-20. Both compounds are unusual in being oxygenated The extraction of three Euryops species and the isolation of euryopsol, C₂₂H₃₀0₄̕̕ are also described. A furanoeremophilane structure containing three hydroxy- groups, one of which is at a bridgehead position, is proposed. Euryopsol is the first furanoeremophilanoid with a substituent attached at C-IO
- Full Text:
- Date Issued: 1971
A structural investigation of the sulphated polysaccharide of Anathaca dentata (suhr) papenf. and the xylan of Chaetangium erinaceum (turn.) papenf.
- Authors: Russell, Irina
- Date: 1972
- Subjects: Polysaccharides , Marine algae -- Composition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4494 , http://hdl.handle.net/10962/d1013103
- Description: Hot-water extraction of Anatheca dentata, a red seaweed belonging to the family Solieriaceae, yielded a mixture of polysaccharides. Fractionation of this mixture with Cetavlon gave a glucomannan as minor component and a highly sulphated major component, which gave D- and L-galactose, D-xylose and small amounts of 3-0 (underscore)-methylgalactose, pyruvic acid and uronic acid on hydrolysis. All subsequent investigations were carried out on the sulphated major component. The sulphate was not labile to alkali, but was removed with methanolic hydrogen chloride. Periodate oxidation of the polysaccharide before and after desulphation indicated that new a-glycol groups were formed during desulphation. All the xylose units in the polymer were cleaved by periodate and this, together with the fact that the major xylose product from methylation analysis of the desulphated polymer was the 2,3, 4-tri-0 (underscore)-methyl derivative, indicated that the xylose occurs as a non-reducing end-group. Methylation of the desulphated polysaccharide revealed the presence of 1,4- and 1,3- linked D- galactose and 1,4- linked L-galactose units in the polymer. D-Glucuronic acid occurred as non-reducing end-groups. Summary, p. 1.
- Full Text:
- Date Issued: 1972
- Authors: Russell, Irina
- Date: 1972
- Subjects: Polysaccharides , Marine algae -- Composition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4494 , http://hdl.handle.net/10962/d1013103
- Description: Hot-water extraction of Anatheca dentata, a red seaweed belonging to the family Solieriaceae, yielded a mixture of polysaccharides. Fractionation of this mixture with Cetavlon gave a glucomannan as minor component and a highly sulphated major component, which gave D- and L-galactose, D-xylose and small amounts of 3-0 (underscore)-methylgalactose, pyruvic acid and uronic acid on hydrolysis. All subsequent investigations were carried out on the sulphated major component. The sulphate was not labile to alkali, but was removed with methanolic hydrogen chloride. Periodate oxidation of the polysaccharide before and after desulphation indicated that new a-glycol groups were formed during desulphation. All the xylose units in the polymer were cleaved by periodate and this, together with the fact that the major xylose product from methylation analysis of the desulphated polymer was the 2,3, 4-tri-0 (underscore)-methyl derivative, indicated that the xylose occurs as a non-reducing end-group. Methylation of the desulphated polysaccharide revealed the presence of 1,4- and 1,3- linked D- galactose and 1,4- linked L-galactose units in the polymer. D-Glucuronic acid occurred as non-reducing end-groups. Summary, p. 1.
- Full Text:
- Date Issued: 1972
A structural investigation of the sulphated polysaccharide pachymenia carnos (J. Ag.) J. Ag.
- Authors: Farrant, Annette J
- Date: 1972
- Subjects: Polysaccharides Red algae -- Composition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4470 , http://hdl.handle.net/10962/d1011785
- Description: The highly sulphated, methylated polysaccharide isolated from Pachymenia Carnosa, a red seaweed, was shown to contain D- galactose, 2-o (underscore) methyl-D- galactose, 6-o (underscore) -methyl- D- galactose and 4-o (underscore)-methylgalactose. The polysaccharide was desulphated with methanolic hydrogen chloride. Methylation of the desulphated polysaccharide revealed that it was composed entirely of (1→73) and (1→4) links in approximately equal amounts. Treatment of the polysaccharide with alkali showed that the majority of the ester sulphate groups were alkali-stable. Partial hydrolysis and acetolysis studies indicated that the polysaccharide was extremely complex, and contained alternate (1→3) and β (1→4) glycosidic linkages. There is evidence for the presence of D-galactose-6-sulphate.
- Full Text:
- Date Issued: 1972
- Authors: Farrant, Annette J
- Date: 1972
- Subjects: Polysaccharides Red algae -- Composition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4470 , http://hdl.handle.net/10962/d1011785
- Description: The highly sulphated, methylated polysaccharide isolated from Pachymenia Carnosa, a red seaweed, was shown to contain D- galactose, 2-o (underscore) methyl-D- galactose, 6-o (underscore) -methyl- D- galactose and 4-o (underscore)-methylgalactose. The polysaccharide was desulphated with methanolic hydrogen chloride. Methylation of the desulphated polysaccharide revealed that it was composed entirely of (1→73) and (1→4) links in approximately equal amounts. Treatment of the polysaccharide with alkali showed that the majority of the ester sulphate groups were alkali-stable. Partial hydrolysis and acetolysis studies indicated that the polysaccharide was extremely complex, and contained alternate (1→3) and β (1→4) glycosidic linkages. There is evidence for the presence of D-galactose-6-sulphate.
- Full Text:
- Date Issued: 1972