Wyniki wyszukiwania - BazTech

1

Badania składu chemicznego żywicopodobnej materii znalezionej w postaci inkluzji w węglu kamiennym

Antkowiak W.Z.

Wiadomości Chemiczne

|

2008

|

[Z] 62, 1-2

115-133

EN

An inhomogeneous resinous material of a yellow to tea-like colour and of an elastic to hard consistency was found as a thin layer inserted between coal seams. An explanation of its origin and chemical composition is now being of particular interest to geologists. The resin was found to be composed of carbon, hydrogen, nitrogen and, by assumption, oxygen. The radiocarbon dating measurement carried out on the raw resin gave a value of 8490 š 50 years BP and an explanation of this result is suggested. Only about one third of the raw resin was soluble in organic solvents at temperatures below 100°C. The etched insoluble amorphous residue that stays solid up to 260°C and reveals carbonyl absorption in IR, when subjected to transesterification in methanol at reflux in the presence of sodium methoxide yielded quantitatively a soluble in chloroform product, which shows an optical activity and proved to be a difficult to separate mixture of methyl esters and alcoholic moiety. The etching of the raw resin with hot water gave an optically inactive mixture of double homologues of poly(oxyethylene)-poly(oxypropylene) glycol structure, that differ one from the other in a number of methylene and oxyethylene groups. The product revealed a characteristic ESI-MS spectrum, the pattern of which could be seen in almost every fraction obtained by extraction of the raw resin with different organic solvents or its transesterification product mixture. The physical properties, other than ESI-MS, showed in the resinous material the presence of some additional components different from polyethylene-polypropylene glycol homologues. The polyurethane character of the resin was demonstrated by identification of bis(4-isocyanatophenyl)methane in the chloroform extract of the raw resin as a secondary product formed in the thermal conditions of GC-MS, and of bis[4-(methoxycarbonylamino)phenyl]methane which occurred in the transesterification product mixture. Additionally, the presence of methyl 9-octadecenoate, accompanied by methyl esters of other fatty acids, was also determined. Finally, after several repeated column and plate chromatographic separations, two "homogeneous" substances of [?]D = +25.7° and +20.2°, respectively, the main components responsible for the optical activity of most resinous fractions, were isolated from the transesterification product mixture. The principal products of these "chromatographically pure" substances turned out to have the adduct structure of methyl ricinoleate and bis(4-isocyanatophenyl)methane. It was proved that in the case of a compound revealing the higher specific rotation, two molecules of methyl ricinoleate were bound, using their OH functions, to one molecule of diisocyanate, giving bis[4-(1-methoxy-1-oxo-9-octadecen-12-yloxycarbonylamino)phenyl]methane. The molecular structure of a compound with lower specific rotation was composed of one molecule of methyl ricinoleate and one molecule of methanol, both bound to diisocyanate to give [4-(1-methoxycarbonylamino)phenyl][4-(1-methoxy-1-oxo-9-octadecen-12-yloxycarbonylamino)phenyl]methane. No components were found of a struc-ture which might indicate the ancient, natural origin of the resinous material. Keywords: resinous inclusions in coal, poly(oxyethylene)-poly(oxypropylene) glycol, double homologue mixture, methyl ricinoleate, urethanes derived from bis(4-isocyanatophenyl)methane, ESI mass spectra.

2

Droga naukowa Profesora Macieja Wiewiórowskiego

Adamiak R.W., Antkowiak W. Z.

Wiadomości Chemiczne

|

2003

|

[Z] 57, 11-12

1001-1037

EN

Professor Dr Maciej Wiewiórowski, the Professor Emeritus at the University of Adam Mickiewicz and at the Institute of Bioorganic Chemistry, Polish Academy of Sciences, a distinguished organic chemist of international authority, truly meritorious in the development of natural product chemistry and the implementation of modern research methods in Poland, celebrates the 85"' anniversary of his birthday this year. In recognition of his remarkable achievements in the field of natural product chemistry, a group of his alumni and former coworkers dedicated to him a symposium (specially organized as a part of the Polish Chemical Society Annual Meeting in Lublin 2003) concerning bioorganic chemistry, the field of science in which his achievements were most significant. Professor M. Wiewiórowski was born August 24, 1918, in Bagatelka, (which is in Poznan’s province). He took up a university course in chemistry in 1936, being interrupted by the World War 11, during which he was deeply engaged in the resistance movement, serving in the Polish underground Home Army, AK, and was kept imprisoned for two years by the German Security Service, SI). He picked up the course again in March, 1945, and received the M.Sc. and Ph.D. in chemistry from Poznań University in 1946 and 1950, respectively. The latter degree he got for his studies of alfa isomerism in codeine chemistry, working under the supervision of Prof. Jerzy Suszko. Professor M. Wiewiórowski got his scientific title of associate professor in 1959 and that of full professor in 1969. From 1946 to 1959, he was employed by the Academy Economics, where he filled numerous high posts and organized a research team working in the natural product chemistry. 1 Ie returned to the university, UAM, in 1959, where he was employed till his retirement in 1989, being the Head of the Stereochemistry Department (1967 1980), the Director of the Institute of Chemistry (1969 1973) and a vice-Rector of A. Mickiewicz University (1968 1972). from 1955, lie was additionally employed by the Polish Academy of Science, being the Head successively of the Biochemical Laboratory in the Plants Cultivation Department (1955 I960), the Biochemistry and Alkaloids Structure Department in IHH (1960 1969), the Natural Product Stereochemistry Department, Inst. Org. ('hem. (1969 1980), the Bioorganic Chemistry Department (1980 1988) and the Bioorganic Chemistry Institute in PASc, as the Director from February to July, 1988, when he retired. In 1965, Professor M. Wiewiórowski heeame an associated member and, in 1977, a full member of the PASc. The numerous scientific contacts with (he most significant chemical and biochemical research centers in the world were initiated by Professor M. Wiewiórowski in 1956 1957, when he was a Follow at the University of Vienna in Professor F. Galinowsky's laboratory and then, twice at the National Research (Council of Canada, Ottawa, in 1959 1960 and 1965 1966, working with Dr. I., Marion. Dr, O.K Edwards and Dr. M. Przybylski. In the late Sixties, lie participated in the formation of a new research center in Poznań, the Intercollegiate Institute of Biochemistry, and, because of his initiative, two other institutions, useful to all the research laboratories in and around Poznań, the Instrumental Chemical Analysis Center and the Doctoral Studios Center, were created at UAM. His first scientific object of interest was the structure of alkaloids, particularly those isolated from lupin plants. Research in this field later evolved into a study of an intramolecular catalysis, the nun of which was to examine the mechanism of the enzyme action, using cyclic diamines as model compounds. His second field of scientific interest, undertaken at the end of the Sixties, was the innovatory on a world scale chemical research of nucleic acids, especially concerning their synthesis, structure elucidation, isolation from plant material and role in peptide synthesis. At the end of the Sixties, he created a new research group, based on the young people working under his supervision at the Institute of Chemistry. UAM, and at the Department of Natural Product Stereochemistry, Inst. Org. Chem., PASc, giving them a special education in the field of nucleic acid chemistry. This group, which was, in 1974, moved from the university to a new place in Noskowskiego Street, where the main chemical mid biochemical laboratories were only built in the following years, very soon readied some significant scientific achievements. Moreover, this group constituted the origin of the independent Department in 198(1, which became the Institute of Bioorganic Chemistry, PASc, in 1988, administered by Professor M. Wiewiórowski all the time till his retirement.

3

Paxillus involutus - grzyb o kontrowersyjnych właściwościach jadalnej olszówki i toksycznego krowiaka podwiniętego

Antkowiak W.Z.

Wiadomości Chemiczne

|

2001

|

[Z] 55, 3-4

245-261

EN

Paxillus involutus, bearing the Polish name olszówka or krowiak podwinięty, is a very common mushroom of a large size, the toxic properties of which revealed much controversy. Besides ordinary people's opinion of the eatability of this mushroom, a number of literature reports showed the fatal consequences of P.involutus consumption. Most often, the symptoms of intoxication shown by different authors concerned changes in the blood, especially those resulting in hemolytic anemia. Although the physiological mechanism of the fatal poisonings was proposed, the toxicity problem is still unsolved because, on the one hand, in many cases the intoxication symptoms have not been observed after mushroom consumption, and, on the other hand, the chemical search for the metabolite responsible for the toxic properties has been unsuccessful up to now. The hitherto obtained results of the research carried out on the chemical composition of P.involutus mainly since the late Sixties of the twentieth century showed the presence of such metabolites as fatty acids, carbohydrates, peptides and other nitrogen containing compounds (including a trace of muscarine) known from their occurrence in other fungi species, as well as of pigments involutine and involutone and presumably two other compounds structurally related to them. All the isolated metabolites and those metabolites whose presence was only suggested on the basis of chromatographic observations are not supposed to be responsible for the toxic properties of P.involututs . Therefore, precise further investigations carried out on the mushroom's chemical composition, including the metabolites enzymatically formed as a response to a mechanical injury of the fruit bodies, seem to be essential.

4

Profesor Maciej Wiewiórowski jako współtwórca nowoczesnych badań chemicznych w Polsce

Antkowiak W.Z.

Wiadomości Chemiczne

|

2000

|

[Z] 54, 11-12

939-947

EN

Professor Maciej Wiewiórowski is one of the most distinguished organic chemists in the world. He got his PhD in 1950 working on the chemical transformations of codeine with Professor J. Suszko at Poznań University. Next, he started developing his own research programme concerning the alkaloid composition of certain Lupinus species. Several of his students then are still continuing the structural and synthetic research in this topic. At the end of the fifties, he spent quite some time on his first long-term post-doctoral fellowship working with Professor Leo Marion in the laboratory of the National Research Council of Canada in Ottawa, and it appeared to be the beginning of his fruitful collaborations with many outstanding scientists in the world in the subsequent years. When working in this foreign laboratory, he took the opportunity to become acquainted with many modern research techniques, especially column chromatography and IR as well as other spectroscopic methods, which enabled him to propagate and popularize these techniques in our country when he returned. In the late sixties, being the Head of the Stereochemistry and Organic Spectrochemistry Division at the Adam Mickiewicz University in Poznań, he began to organize, under the auspices of the Polish Academy of Science, a new field of research in Poland, then undeveloped worldwide, concerning the synthesis of nucleic acids. He both gathered young scientists, giving them special training, and organized new laboratories outside the University. In the early seventies, he moved with his group to the tentative laboratories at Noskowskiego Street in Poznań, there systematically and intensively expanding this research center, which finally resulted in the creation of the Institute of Bioorganic Chemistry of the PASc, a leader in the scientific world in carrying out modern biochemical research in nucleic acid as well as in protein chemistry. During recent years, already being retired, he is still very active in the life of the Institute , including carrying out research mainly on the reaction of nucleosides in a solid state.

5

Wspomnienia o profesorze Jerzym Suszce i szkic jego dokonań naukowych

Antkowiak W.Z.

Wiadomości Chemiczne

|

1998

|

[Z] 52, 7-8

473-509

EN

A quarter of a century has already passed since the most distinguished Polish pioneer in both natural products chemistry and stereochemistry, scientist meritorious for chemistry education, Professor Jerzy Suszko, passed away. He was born in Silesia near Teschen in 1889 and studied at the Polytechnic of Prague where he finished his PhD thesis under the auspices of Paul Rabe at the age of 24. After World War I he took on research work at the Jagielloński University in Cracow collaborating with Karol Dziewoński at the beginning. Next, after passing a habilitation examination and spending three years at the Univerity of Lvov, he moved to Poznań, where he spent the second half of his life, working as a professor and the Head of the Organic Chemistry Department of the University of Poznań. Furthermore, he was to become the Head of the Laboratory of Alkaloids of the Institute of Organic Chemistry of the Polish Academy of Sciences. He also held some highly responsible and a Dean of the Mathematical and Natural Science Faculty for a few years. The main scientific achievements of Professor Jerzy Suszko were concerned with the chemistry of physiologically active natural products and with the spatial structure of organic molecules. From among the natural products, the alkaloids and especially those of cinchona bark were the most intensively studied mainly because of their pharmacological properties. His synthetic and structural studies analysed all the most reactive and stereochemically important fragments of the molecules of quinine and related alkaloids. This resulted analogues differing by the kind of substituent in the quinoline moiety as well as the corresponding stereoisomers. Further significant achievements in the same field comprised, among others, the elaboration of a convenient method of a reverse conversion of quinotoxine (the product of an acid treatment of quinine but also occurring as the key intermediate in the quinine synthesis) and related toxins to the natural cinchona alkaloids, the determination of the pattern of rearrangement within the vicinal amino-alcohol fragment, and the discoveries in the chemistry of derivatives with a modified vinyl side chain, especially those being intramolecular ethers. The structure and conversion studies of other alkaloids concerned those occurring in the genera Papaver (codeine and rheadine), Lupinus and Cortinarius. At the beginning of the thirties, J. Suszko, proposed a new method of determining the molecular symmetry, especially in the case of fused-ring polycyclic aromatic hydrocarbons. This method was next verified mainly on naphthalene molecules and was based on the binding of two identical chiral substituents to the ring system in different positions followed by an analysis of the resulting stereochemical mixture. Other stereochemical studies concerning stereocontrolled syntheses, conformation stability and configuration determination were carried out on various cyclic apliphatic hydrocarbons, including bornane derivatives. Professor Jerzy Suszko educated a great number of graduated students both in chemistry and pharmacy. From about forty people who got their PhD degrees under his scientific supervision many later reached the highest levels in their scientific careers. He was a founding member of the Polish Chemical Society and was very much engaged in its activities during his whole life. He served in some responsible offices therein, including the President of the Society. He was also a member of several foreign scientific societies, including the American Chemical Society.