- Email: [email protected]
Albert Zlatkis
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ALBERT ZLATKIS
ALBERT ZLATKIS was born i n 1924 i n Pomorzany, Poland and e m i g r a t e d t o Canada a t t h e age o f t h r e e . H e r e c e i v e d a B.A.Sc. d e g r e e i n Chemi c a l E n g i n e e r i n g from t h e U n i v e r s i t y of Toronto i n 1947 and a M.A.Sc. a t t h e same s c h o o l i n 1948. H i s Ph.D. was o b t a i n e d from Wayne S t a t e U n i v e r s i t y i n 1952. A f t e r one y e a r of p o s t - d o c t o r a l work on a Michigan Heart A s s o c i a t i o n F e l l o w s h i p he j o i n e d t h e S h e l l O i l Company i n Houston, Texas a s a research chemist. D r . Z l a t k i s joined t h e f a c u l t y o f t h e U n i v e r s i t y o f Houston i n 1955 a s a s s i s t a n t p r o f e s s o r o f c h e m i s t r y . H e became chairman o f t h e department i n 1958 f o r f o u r y e a r s and was a p p o i n t e d p r o f e s s o r i n 1963. D r . Z l a t k i s i s t h e a u t h o r o f more t h a n 150 s c i e n t i f i c p a p e r s . H i s r e s e a r c h i n t e r ests include c l i n i c a l chemistry, c a p i l l a r y chromatography, f l a v o r a n a l y s i s , i o n i z a t i o n d e t e c t o r s , c o n c e n t r a t i o n t e c h n i q u e s , environmental a n a l y s i s and g a s chromatography-mass s p e c t r o metry s t u d i e s o f p r o f i l e s o f v o l a t i l e m e t a b o l i t e s o f b i o l o g i c o r i g i n . H e i s t h e co-author o f A Concise Introduction t o Organic Chemistry and h a s c o e d i t e d s e v e r a l books such a s The Practice of Gas Chromatography, Preparative Gas Chromatography and High Performance Thin-Layer Chromatography. D r . Z l a t k i s h a s been e d i t o r of Advances i n Chromatography s i n c e i t s i n c e p t i o n i n 1963. H e i s on t h e e d i t o r i a l board of JournaZ
of Chromatography, Chromatographia, Journal of and J o m a 2 of High Resolution Chromatography.
Chromatographic Science
D r . Z l a t k i s r e c e i v e d t h e American Chemi'cal S o c i e t y Award i n Chromatography i n 1973. H e w a s a l s o honored w i t h t h e NASA Technology Award i n 1975 and 1978. H e h a s l e c t u r e d i n t h e U.S.S.R. and Poland under t h e a u s p i c e s of t h e i r Academies o f S c i e n c e s and h a s been a t o u r s p e a k e r f o r t h e South A f r i c a n Chemical S o c i e t y . D r . Z l a t k i s has been a c t i v e l y engaged i n chromatography s i n c e 1954. H e o r g a n i z e d t h e I n t e r n a t i o n a l Symposium on Advances i n Chromatography i n 1963 and h a s been i t s chairman f o r t h e twelve m e e t i n g s t o d a t e .
474 During my senior year as a student in chemical engineering at the University of Toronto, I was introduced to an area of research which was to have a deep impact on both my technical and social life. In the fall of 1947 I was assigned to carry out a research problem under Don McArthur who was studying the oxidation of trans decalin for his doctoral research. The location of the laboratory seemed a return to nineteenth century conditions since it was in a sub-basement in the Mining Building and was affectionately called the “coal hole“. It was here that I started my journey into separation science. The problem involved isomerization of commercial decalin, a mixture of cis-tr4uns isomers, into the predominately trans form and then the fractionation of the pure isomers by the use of Stedman distillation columns. Although the literature indicated that the isomerization proceeded easily with anhydrous aluminium chloride, I was unable to effect this simple conversion. It was only after I had tried my sixth brand of aluminium chloride that any success was evident. This was from an old bottle which had its origin in Germany. Fortunately the label was still readable and I noted the presence of ferric chloride as an impurity. Indeed it was this extra trace compound which was promoting the isomerization. Although a minor achievement it was this experiment which turned my interest from engineering to chemistry. After obtaining my master’s degree I decided to accept a fellowship at Wayne State University in Detroit and proceeded to work in
Fig. 56.1. A. Zlatkis, at the University of Toronto, Canada, in 1947.
475 organic synthesis under A.J. Boyle. It was here that I met Bennie Zak with whom I collaborated to develop a procedure for the determination of cholesterol in blood serum ( 1 ) and this interest in clinical chemistry has continued to the present. Graduation led to a position as research chemist with the Shell Oil Company in Houston, Texas, and my introduction to chromatography. At that time I joined the analytical group to become familiar with all of the techniques used and involved in analyzing the products of hydroprocessing. In 1954 Lloyd Snyder joined this group and shortly thereafter Mr. Zuiderweg of Shell in Amsterdam was visiting Houston and excited us with the news of the development of gas chromatography by Martin and James. Our group immediately started building an instrument and in a few months we were making hydrocarbon separations on 50-ft. packed columns. I had been teaching organic chemistry on a part-time basis at the University of Houston and enjoyed this academic contact although I must say that my time spent at the University and some long evenings in the library made it difficult for my wife Esther. She has indeed been patient for a long period - since our early days in Canada. In August of 1955 I was invited t o join the chemistry department of the University of Houston as an assistant professor and I readily accepted. Since I was interested in stereochemistry and had an experimental background in gas chromatography, I decided to attempt to solve a classical problem, i.e., to separate the enantiomers of a compound which contained an asymmetric nitrogen atom. This seemed feasible for an aziridine molecule from an energetic viewpoint, but low temperature would be necessary. Gas chromatography should provide the answer using an optically active stationary phase. 2-Brucine, an alkaloid was dissolved in quinoline and the chiral column was ready. Although the procedure seems rather simple we had to make our own chromatographic supports and this involved obtaining one firebrick from Johns-Manville, crushing, washing and sieving this material. Hamilton syringes had not yet been invented and micro-dippers were used. Three months were spent in attempting the resolution of amines I continued to work with the same chromatographic without success column since it showed some interesting selectivity in making hydrocarbon separations. After submitting my first manuscript ( 2 ) on this topic to Analytical Chemistry, I attended an I.S.A. symposium on Gas Chromatography at Lansing, Michigan in August 1957. Here I met two outstanding young men who were already pioneers in the field Tony James and Courtenay Phillips. The third of these symposia was in 1961 and several of my colleagues urged me to organize a meeting
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*In collaboration with Dr. V. Schurig of the University of Tiibingen we have just recently solved this problem. Resolution of l-chloro2,2-dimethylaziridine was resolved using a 100 m x 0.5 mm nickel capillary column coated with an optically active nickel complex of 3-trifluoroacetyl camphorate. The separation factor of 1.43 was indeed large.
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i n Houston which would improve t h e e x i s t i n g symposia, i . e . by h a v i n g more s p e a k e r s from Europe where m o s t o f t h e developments were b e i n g made, p a p e r s which w e r e reviewed b e f o r e b e i n g p r e s e n t e d and p u b l i c a t i o n of t h e s e p a p e r s i n a j o u r n a l . Sandy Lipsky o f t h e Yale U n i v e r s i t y School of Medicine w a s a l r e a d y e s t a b l i s h e d i n g a s chromatography,
F i g . 56.2. M i a m i Beach Symposium, J u n e 2 , 1970. Standing: ( l e f t - t o - r i g h t ) A. Z l a t k i s , I . Halhsz, A . I . M . Keulemans, C . G u i l l e m i n , L.S. E t t r e . S e a t e d : K i t t y E t t r e , Agnes Halhsz and E s t h e r Zlatkis. p r i m a r i l y i n t h e area o f l i p i d s e p a r a t i o n s , and i t w a s h e who f i n a l l y convinced m e t o f o r m a l i z e t h e I n t e r n a t i o n a l Symposium on Advances i n G a s Chromatography. The f i r s t m e e t i n g h e l d i n Houston, J a n u a r y 21-24, 1963 was i n d e e d a memorable one. I t was a l s o t h e b e g i n n i n g o f c l o s e f r i e n d s h i p s w i t h many of t h e l e a d i n g s c i e n t i s t s i n t h i s f i e l d . A l l 23 p a p e r s p r e s e n t e d a t t h e m e e t i n g w e r e reviewed and p u b l i s h e d i n t h e A p r i l i s s u e o f AnaZyticaZ Chemistry, a r a t h e r new e x p e r i e n c e f o r t h i s j o u r n a l and i t s e d i t o r L a r r y H a l l e t t . The Houston symposium had a n unusual g e n e s i s . A f i e r c e w i n t e r storm had c l o s e d many o f t h e major a i r p o r t s and t r a v e l was n e x t t o i m p o s s i b l e . Houston i t s e l f had one o f i t s rare snow and i c e s p e c t a c u l a r s . On t h e e v e o f t h e meeting o n l y 50 of t h e d e l e g a t e s had a r r i v e d a t t h e S h e r a t o n Hotel and s e r i o u s c o n s i d e r a t i o n w a s g i v e n t o a one-day postponement. By s i x o ' c l o c k i n t h e morning a l l 600 had a r r i v e d and t h e symposium was i t s way t h r e e h o u r s l a t e r .
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F i g . 56.3. Symposium a t L a s Vegas, Caesars' P a l a c e , J a n u a r y 2 0 , 1969. L e f t t o r i g h t : P e a r l L i p s k y , S.R. Lipsky, C . G . S c o t t , A. Z l a t k i s , R.S. Evans and Vicki S c o t t . Each symposium seems t o have had unusual moments which c a n b e r e a d i l y r e c a l l e d . A t t h e morning s e s s i o n o f o u r f i r s t meeting, D r s . Bayer, Schomburg and Halksz had j u s t a r r i v e d from Germany, t h e f i r s t two v i s i t i n g t h e U.S.A. f o r t h e f i r s t t i m e . They s a t i n amazement a s Herman F e l t o n opened his l e c t u r e w i t h a song about g a s chromatography. The second symposium was a l s o h e l d i n Houston i n A p r i l 1964 and d u r i n g a r e c e p t i o n a t t h e home o f Marjorie and Evan H o m i n g one o f t h e Dutch s c i e n t i s t s , J . Pypker, walked t h r o u g h a g l a s s w a l l . O t h e r i n c i d e n t s come t o mind such a s t h e meeting i n New York where one e v e n i n g a t L i n d y ' s , P r o f e s s o r Bayer o r d e r e d a l l o f t h e food f o r a group o f 12 and f o r g o t t o p l a c e h i s own o r d e r ; however, h e d i d manage t o r e c e i v e t h e b i l l . I n M i a m i Beach, one o f t h e s p e a k e r s from F i n l a n d gave h i s l e c t u r e wearing a t e r r y c l o t h r o b e and s h o r t s and p r e s e n t e d r o s e s t o two of h i s f r i e n d s p r i o r t o t h e t a l k . A r t h u r Karmen o f t h e A l b e r t E i n s t e i n C o l l e g e o f Medicine, a c o n s t a n t cont r i b u t o r t o t h e s e symposia, h a s always r e l a x e d h i s a u d i e n c e w i t h some w e l l chosen s t o r i e s . Two meetings were h e l d i n Las Vegas and i t was h e r e t h a t Sandy Lipsky showed a s k i l l a t t h e t a b l e s t h a t w a s matched o n l y by h i s s c i e n t i f i c endeavors. I t w a s a l s o a t C a e s a r s ' P a l a c e i n L a s Vegas where a t h e s i s w a s p r e s e n t e d and defended by P a t Howard - i t seemed i t w a s t h e o n l y p l a c e t h a t a l l o f t h e p r o f e s s o r s on h i s committee c o u l d b e g a t h e r e d t o g e t h e r . P r o f e s s o r Bayer and I had p r e v i o u s l y v i s i t e d L a s Vegas i n 1966. On t h i s o c c a s i o n w e were accorded a r o y a l welcome a t t h e T o u r i s t Bureau s i n c e w e were t h e 1 , 0 0 0 , 0 0 0 t h v i s i t o r .
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F i g . 5 6 . 4 . P a t Howard d e f e n d i n g h i s t h e s i s d u r i n g t h e symposium a t L a s Vegas, C a e s a r s ' P a l a c e , on December 2 , 1971. S t a n d i n g : P.Y. Howard, s e a t e d : J . O r o , E. Gil-Av, W.E. Wentworth, J . L . Bear, W . P a r r , A . Z l a t k i s , and B. H a l p e r n . O t h e r symposia h a v e been h e l d i n T o r o n t o , Munich and Amsterdam. The l a t t e r had a r e c e p t i o n a t t h e Rijksmuseum amongst t h e Rembrandts, Vermeers and F r a n s H a l s ' . A p e r s o n a l t r i b u t e from some of my c o l l e a g u e s a t t h e Munich m e e t i n g w i l l always b e remembered. A s I l a t e r found o u t , t h e o r i g i n a l s c r o l l they had prepared w a s l o s t i n t h e o v e r s e a s m a i l and i t had t o b e r e p l a c e d a t t h e l a s t m i n u t e . Among t h e f o r e i g n s c i e n t i s t s who have c o n t r i b u t e d h e a v i l y t o t h e s u c c e s s o f t h e s e i n t e r n a t i o n a l symposia a r e V i c t o r P r e t o r i u s o f South A f r i c a , Denis D e s t y , Howard P u r n e l l , Tony James, C h a r l e s Brooks and John Knox o f t h e U n i t e d Kingdom, George Guiochon o f F r a n c e , E r n s t B a y e r , G e r h a r d Schomburg and Rudolf Kaiser o f Germany, J o s e f Huber of A u s t r i a and p a r t i c u l a r m e n t i o n s h o u l d b e made o f a "Hungarian q u a r t e t " : L e s l i e E t t r e (U.S.A.) I s t v h n H a l h s z (Germany), Csaba Horvkth (U.S.A.) and E r v i n KovP s ( S w i t z e r l a n d ) who are e s t a b l i s h e d i n v e s t i g a t o r s i n chromatography Many o f t h e s e h a v e been honored w i t h t h e T s w e t t Chromatography medal which w a s i n t r o d u c e d a t t h e 1974 Symposium i n Houston. The r e n n a i s s a n c e o f l i q u i d chromatography i n 1966 h a s b r o u g h t many o f t h e g a s chromatography s p e c i a l i s t s i n t o new f r o n t i e r s . Among o t h e r s , D r s . H a l i s z , H o r v h t h , Knox, K i r k l a n d , Huber and S c o t t have made t h i s t r a n s i t i o n e f f o r t l e s s l y . I t now a p p e a r s t h a t t h i n - l a y e r chromatography w i l l a l s o h a v e a s e c o n d g e n e r a t i o n of r e s e a r c h and development. T h e r e i s p r o b a b l y no one i n d i v i d u a l who i n f l u e n c e d t h e c o u r s e o f my career more t h a n t h e E n g l i s h s c i e n t i s t J i m Lovelock. My f i r s t a w a r e n e s s o f t h i s g e n t l e man w a s t h r o u g h h i s p a p e r on t h e a r g o n i o n i z a t i o n d e t e c t o r which w a s p u b l i s h e d i n t h e f i r s t i s s u e o f t h e Jouu*na2 of Chromatography i n 1958. I n t h e f a l l of t h a t y e a r I l e a r n e d
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Fig. 56.5. Las Vegas, 1966. A. Zlatkis and E. Bayer at the tourist bureau. that he was planning to spend some time in Dr. Lipsky's laboratory at Yale. Shortly after his arrival in the U.S.A. I called New Haven and asked him to visit me in Houston. I was pleasantly surprised when he accepted and it was only much later that I learned that Jim has always had difficulty refusing invitations by telephone. We spent an exciting week working to assemble a capillary chromatographic system and then published the first American paper on this subject (3). This was the beginning of a long personal and professional relationship with Jim Lovelock, much of our collaboration involving ionization detectors. In 1975 Jim was awarded a Tswett Medal for his outstanding contributions to chromatography. Special mention should be made of Professor A.J.P. Martin whose genius has been responsible for the direction of many careers. He has made profound contributions to all fields of chemistry over the past 45 years. His work has ranged from research in vitamin deficiencies, factors controlling insulin secretion and the production of penicillin to the development of liquid partition chromatography, the invention of paper chromatography, the development of displacement electrophoresis and above all the invention of gas chromatography. If one considers the problems scientists would face working in the field of chemistry without the techniques of paper chromatography, liquid partition chromatography, and gas chromatography, one begins to realize the tremendous impact of this man's work in science today. Very few laboratories indeed do not possess the gas chromatograph, an instrument which is an ever present monument to Dr. Martin's innovative achievements and scientific contributions.
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F i g . 56.6. Symposium a t Houston, O c t o b e r 30, 1976. S t a n d i n g ( l e f t - t o - r i g h t ) U t e H e z e l , C . M e r r i t t , C. G u i l l e m i n , M . J . E . Golay, G . D i j k s t r a , R.E. Sievers. Seated: Esther Zlatkis, A. Zlatkis. Although a volume c o u l d be w r i t t e n p e r t a i n i n g t o my p e r s o n a l r e m i n i s c e n c e s of D r . Archer M a r t i n , one i n c i d e n t may b e o f i n t e r e s t . A f t e r c o n v i n c i n g him t o j o i n t h e U n i v e r s i t y o f Houston i n 1974, a f o r m a l i t y o f o b t a i n i n g a l i s t o f h i s p u b l i c a t i o n s w a s r e q u i r e d . When I v i s i t e d Archer a t Abbotsbury - a medieval c a s t l e i n London, - I asked him f o r t h i s l i s t . S i n c e one d i d n o t e x i s t h e s u g g e s t e d he c o u l d s u p p l y some of t h e r e p r i n t s . An a n c i e n t c a b i n e t d i s c l o s e d a l a r g e number o f unopened packages c o n t a i n i n g r e p r i n t s i n c l u d i n g h i s f i r s t p u b l i c a t i o n i n 1931 e n t i t l e d "On a New Method o f D e t e c t i n g P y r o e l e c t r i c i t y " . I c o l l e c t e d t h e n e c e s s a r y r e p r i n t s and w a s a b l e t o assemble t h e r e q u i r e d l i s t . I t may b e o f i n t e r e s t t o n o t e t h a t h i s n i n t h p a p e r p u b l i s h e d i n 1941 on p a r t i t i o n chromatography a t t h e age o f 30 paved t h e way f o r h i s Nobel P r i z e . Twenty y e a r s have p a s s e d s i n c e my f i r s t chromatography p a p e r and d u r i n g t h i s t i m e my e f f o r t s have been d i r e c t e d i n t o some f a i r l y d i v e r s e areas. These i n c l u d e c a p i l l a r y columns, i o n i z a t i o n d e t e c t o r s , flow programming, a n a l y s i s o f lunar m a t e r i a l s , and f l a v o r c o n s t i t u e n t s o f c o f f e e , c h e e s e s and mushrooms. I n r e c e n t y e a r s t h e environment and b i o l o g i c a l f l u i d s have a t t r a c t e d o u r a t t e n t i o n . N e w t e c h n i q u e s have been developed f o r t h e c o n c e n t r a t i o n o f o r g a n i c v o l a t i l e s by u s i n g a hydrophobic porous polymer Tenax ( 2 , g - d i p h e n y l polyphenylene o x i d e ) ( 4 ) . The a n a l y s i s of t r a c e o r g a n i c c o n s t i t u e n t s ( 5 , 6 ) i n a i r ,
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Fig. 56.7. At the University of Houston, in 1961: J.E. Lovelock and A . Zlatkis examining new ionization detector designs.
Fig. 56.8. Presentation of the Tswett Chromatography Medal to J.E. Lovelock at Munich, November 3, 1975. L.S. Ettre, A. Zlatkis and J.E. Lovelock.
482 water, u r i n e , serum, s a l i v a and c e r e b r o s p i n a l f l u i d are now r e a d i l y o b t a i n e d . I n c o l l a b o r a t i o n w i t h D r . Hartmut L i e b i c h o f Tubingen, Germany, w e have b e e n a b l e t o d e t e r m i n e a number o f s i g n i f i c a n t m e t a b o l i t e s which a r e i m p o r t a n t i n t h e d i a g n o s i s o f diabetes m e l l i t u s M e t a b o l i c p r o f i l e s are p r e s e n t l y b e i n g d e v e l o p e d f o r s e v e r a l o t h e r diseases ( 7 ) . These y e a r s h a v e been most e v e n t f u l and e x c i t i n g , y i e l d i n g many f r i e n d s h i p s from a l l p a r t s o f t h e g l o b e . I n p a r t i c u l a r , my c o l l a b o r a t i o n w i t h L e s l i e E t t r e , o u r r e s i d e n t h i s t o r i a n o f chromatography, i n e d i t i n g many books and o r g a n i z i n g t h e i n t e r n a t i o n a l symposia h a s i n d e e d been a r e w a r d i n g o n e . REFERENCES 1 A . Z l a t k i s , B. Zak and A . J . Boyle, J. Lab. CZin. Med. 4 1 (1953) 486. 2 A . Z l a t k i s , Anal. Chem. 30 (1958) 332. 3 A . Z l a t k i s and J . E . Lovelock, Anal. Chem. 31 (1959) 620. 4 A . Z l a t k i s , H . A . L i c h t e n s t e i n and A . T i s h b e e , Chromatographia 6 (1973) 6 7 . 5 K . Y . L e e , D. Nurok and A . Z l a t k i s , J. Chromatogr. 158 (1978) 377 6 G . H o l z e r , H . S h a n f i e l d , A . Z l a t k i s , W. B e r t s c h , P . J u a r e z , H. Mayfield and H.M. L i e b i c h , J. Chromatogr. 1 4 2 (1977) 755. 7 H . M . L i e b i c h , O . A l - B a b b i l i , A . Z l a t k i s and K . K i m , CZin. Chem. 212 (1975) 294.
ALBERT ZLATKIS
ALBERT ZLATKIS was born i n 1924 i n Pomorzany, Poland and e m i g r a t e d t o Canada a t t h e age o f t h r e e . H e r e c e i v e d a B.A.Sc. d e g r e e i n Chemi c a l E n g i n e e r i n g from t h e U n i v e r s i t y of Toronto i n 1947 and a M.A.Sc. a t t h e same s c h o o l i n 1948. H i s Ph.D. was o b t a i n e d from Wayne S t a t e U n i v e r s i t y i n 1952. A f t e r one y e a r of p o s t - d o c t o r a l work on a Michigan Heart A s s o c i a t i o n F e l l o w s h i p he j o i n e d t h e S h e l l O i l Company i n Houston, Texas a s a research chemist. D r . Z l a t k i s joined t h e f a c u l t y o f t h e U n i v e r s i t y o f Houston i n 1955 a s a s s i s t a n t p r o f e s s o r o f c h e m i s t r y . H e became chairman o f t h e department i n 1958 f o r f o u r y e a r s and was a p p o i n t e d p r o f e s s o r i n 1963. D r . Z l a t k i s i s t h e a u t h o r o f more t h a n 150 s c i e n t i f i c p a p e r s . H i s r e s e a r c h i n t e r ests include c l i n i c a l chemistry, c a p i l l a r y chromatography, f l a v o r a n a l y s i s , i o n i z a t i o n d e t e c t o r s , c o n c e n t r a t i o n t e c h n i q u e s , environmental a n a l y s i s and g a s chromatography-mass s p e c t r o metry s t u d i e s o f p r o f i l e s o f v o l a t i l e m e t a b o l i t e s o f b i o l o g i c o r i g i n . H e i s t h e co-author o f A Concise Introduction t o Organic Chemistry and h a s c o e d i t e d s e v e r a l books such a s The Practice of Gas Chromatography, Preparative Gas Chromatography and High Performance Thin-Layer Chromatography. D r . Z l a t k i s h a s been e d i t o r of Advances i n Chromatography s i n c e i t s i n c e p t i o n i n 1963. H e i s on t h e e d i t o r i a l board of JournaZ
of Chromatography, Chromatographia, Journal of and J o m a 2 of High Resolution Chromatography.
Chromatographic Science
D r . Z l a t k i s r e c e i v e d t h e American Chemi'cal S o c i e t y Award i n Chromatography i n 1973. H e w a s a l s o honored w i t h t h e NASA Technology Award i n 1975 and 1978. H e h a s l e c t u r e d i n t h e U.S.S.R. and Poland under t h e a u s p i c e s of t h e i r Academies o f S c i e n c e s and h a s been a t o u r s p e a k e r f o r t h e South A f r i c a n Chemical S o c i e t y . D r . Z l a t k i s has been a c t i v e l y engaged i n chromatography s i n c e 1954. H e o r g a n i z e d t h e I n t e r n a t i o n a l Symposium on Advances i n Chromatography i n 1963 and h a s been i t s chairman f o r t h e twelve m e e t i n g s t o d a t e .
474 During my senior year as a student in chemical engineering at the University of Toronto, I was introduced to an area of research which was to have a deep impact on both my technical and social life. In the fall of 1947 I was assigned to carry out a research problem under Don McArthur who was studying the oxidation of trans decalin for his doctoral research. The location of the laboratory seemed a return to nineteenth century conditions since it was in a sub-basement in the Mining Building and was affectionately called the “coal hole“. It was here that I started my journey into separation science. The problem involved isomerization of commercial decalin, a mixture of cis-tr4uns isomers, into the predominately trans form and then the fractionation of the pure isomers by the use of Stedman distillation columns. Although the literature indicated that the isomerization proceeded easily with anhydrous aluminium chloride, I was unable to effect this simple conversion. It was only after I had tried my sixth brand of aluminium chloride that any success was evident. This was from an old bottle which had its origin in Germany. Fortunately the label was still readable and I noted the presence of ferric chloride as an impurity. Indeed it was this extra trace compound which was promoting the isomerization. Although a minor achievement it was this experiment which turned my interest from engineering to chemistry. After obtaining my master’s degree I decided to accept a fellowship at Wayne State University in Detroit and proceeded to work in
Fig. 56.1. A. Zlatkis, at the University of Toronto, Canada, in 1947.
475 organic synthesis under A.J. Boyle. It was here that I met Bennie Zak with whom I collaborated to develop a procedure for the determination of cholesterol in blood serum ( 1 ) and this interest in clinical chemistry has continued to the present. Graduation led to a position as research chemist with the Shell Oil Company in Houston, Texas, and my introduction to chromatography. At that time I joined the analytical group to become familiar with all of the techniques used and involved in analyzing the products of hydroprocessing. In 1954 Lloyd Snyder joined this group and shortly thereafter Mr. Zuiderweg of Shell in Amsterdam was visiting Houston and excited us with the news of the development of gas chromatography by Martin and James. Our group immediately started building an instrument and in a few months we were making hydrocarbon separations on 50-ft. packed columns. I had been teaching organic chemistry on a part-time basis at the University of Houston and enjoyed this academic contact although I must say that my time spent at the University and some long evenings in the library made it difficult for my wife Esther. She has indeed been patient for a long period - since our early days in Canada. In August of 1955 I was invited t o join the chemistry department of the University of Houston as an assistant professor and I readily accepted. Since I was interested in stereochemistry and had an experimental background in gas chromatography, I decided to attempt to solve a classical problem, i.e., to separate the enantiomers of a compound which contained an asymmetric nitrogen atom. This seemed feasible for an aziridine molecule from an energetic viewpoint, but low temperature would be necessary. Gas chromatography should provide the answer using an optically active stationary phase. 2-Brucine, an alkaloid was dissolved in quinoline and the chiral column was ready. Although the procedure seems rather simple we had to make our own chromatographic supports and this involved obtaining one firebrick from Johns-Manville, crushing, washing and sieving this material. Hamilton syringes had not yet been invented and micro-dippers were used. Three months were spent in attempting the resolution of amines I continued to work with the same chromatographic without success column since it showed some interesting selectivity in making hydrocarbon separations. After submitting my first manuscript ( 2 ) on this topic to Analytical Chemistry, I attended an I.S.A. symposium on Gas Chromatography at Lansing, Michigan in August 1957. Here I met two outstanding young men who were already pioneers in the field Tony James and Courtenay Phillips. The third of these symposia was in 1961 and several of my colleagues urged me to organize a meeting
-
*.
*In collaboration with Dr. V. Schurig of the University of Tiibingen we have just recently solved this problem. Resolution of l-chloro2,2-dimethylaziridine was resolved using a 100 m x 0.5 mm nickel capillary column coated with an optically active nickel complex of 3-trifluoroacetyl camphorate. The separation factor of 1.43 was indeed large.
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i n Houston which would improve t h e e x i s t i n g symposia, i . e . by h a v i n g more s p e a k e r s from Europe where m o s t o f t h e developments were b e i n g made, p a p e r s which w e r e reviewed b e f o r e b e i n g p r e s e n t e d and p u b l i c a t i o n of t h e s e p a p e r s i n a j o u r n a l . Sandy Lipsky o f t h e Yale U n i v e r s i t y School of Medicine w a s a l r e a d y e s t a b l i s h e d i n g a s chromatography,
F i g . 56.2. M i a m i Beach Symposium, J u n e 2 , 1970. Standing: ( l e f t - t o - r i g h t ) A. Z l a t k i s , I . Halhsz, A . I . M . Keulemans, C . G u i l l e m i n , L.S. E t t r e . S e a t e d : K i t t y E t t r e , Agnes Halhsz and E s t h e r Zlatkis. p r i m a r i l y i n t h e area o f l i p i d s e p a r a t i o n s , and i t w a s h e who f i n a l l y convinced m e t o f o r m a l i z e t h e I n t e r n a t i o n a l Symposium on Advances i n G a s Chromatography. The f i r s t m e e t i n g h e l d i n Houston, J a n u a r y 21-24, 1963 was i n d e e d a memorable one. I t was a l s o t h e b e g i n n i n g o f c l o s e f r i e n d s h i p s w i t h many of t h e l e a d i n g s c i e n t i s t s i n t h i s f i e l d . A l l 23 p a p e r s p r e s e n t e d a t t h e m e e t i n g w e r e reviewed and p u b l i s h e d i n t h e A p r i l i s s u e o f AnaZyticaZ Chemistry, a r a t h e r new e x p e r i e n c e f o r t h i s j o u r n a l and i t s e d i t o r L a r r y H a l l e t t . The Houston symposium had a n unusual g e n e s i s . A f i e r c e w i n t e r storm had c l o s e d many o f t h e major a i r p o r t s and t r a v e l was n e x t t o i m p o s s i b l e . Houston i t s e l f had one o f i t s rare snow and i c e s p e c t a c u l a r s . On t h e e v e o f t h e meeting o n l y 50 of t h e d e l e g a t e s had a r r i v e d a t t h e S h e r a t o n Hotel and s e r i o u s c o n s i d e r a t i o n w a s g i v e n t o a one-day postponement. By s i x o ' c l o c k i n t h e morning a l l 600 had a r r i v e d and t h e symposium was i t s way t h r e e h o u r s l a t e r .
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F i g . 56.3. Symposium a t L a s Vegas, Caesars' P a l a c e , J a n u a r y 2 0 , 1969. L e f t t o r i g h t : P e a r l L i p s k y , S.R. Lipsky, C . G . S c o t t , A. Z l a t k i s , R.S. Evans and Vicki S c o t t . Each symposium seems t o have had unusual moments which c a n b e r e a d i l y r e c a l l e d . A t t h e morning s e s s i o n o f o u r f i r s t meeting, D r s . Bayer, Schomburg and Halksz had j u s t a r r i v e d from Germany, t h e f i r s t two v i s i t i n g t h e U.S.A. f o r t h e f i r s t t i m e . They s a t i n amazement a s Herman F e l t o n opened his l e c t u r e w i t h a song about g a s chromatography. The second symposium was a l s o h e l d i n Houston i n A p r i l 1964 and d u r i n g a r e c e p t i o n a t t h e home o f Marjorie and Evan H o m i n g one o f t h e Dutch s c i e n t i s t s , J . Pypker, walked t h r o u g h a g l a s s w a l l . O t h e r i n c i d e n t s come t o mind such a s t h e meeting i n New York where one e v e n i n g a t L i n d y ' s , P r o f e s s o r Bayer o r d e r e d a l l o f t h e food f o r a group o f 12 and f o r g o t t o p l a c e h i s own o r d e r ; however, h e d i d manage t o r e c e i v e t h e b i l l . I n M i a m i Beach, one o f t h e s p e a k e r s from F i n l a n d gave h i s l e c t u r e wearing a t e r r y c l o t h r o b e and s h o r t s and p r e s e n t e d r o s e s t o two of h i s f r i e n d s p r i o r t o t h e t a l k . A r t h u r Karmen o f t h e A l b e r t E i n s t e i n C o l l e g e o f Medicine, a c o n s t a n t cont r i b u t o r t o t h e s e symposia, h a s always r e l a x e d h i s a u d i e n c e w i t h some w e l l chosen s t o r i e s . Two meetings were h e l d i n Las Vegas and i t was h e r e t h a t Sandy Lipsky showed a s k i l l a t t h e t a b l e s t h a t w a s matched o n l y by h i s s c i e n t i f i c endeavors. I t w a s a l s o a t C a e s a r s ' P a l a c e i n L a s Vegas where a t h e s i s w a s p r e s e n t e d and defended by P a t Howard - i t seemed i t w a s t h e o n l y p l a c e t h a t a l l o f t h e p r o f e s s o r s on h i s committee c o u l d b e g a t h e r e d t o g e t h e r . P r o f e s s o r Bayer and I had p r e v i o u s l y v i s i t e d L a s Vegas i n 1966. On t h i s o c c a s i o n w e were accorded a r o y a l welcome a t t h e T o u r i s t Bureau s i n c e w e were t h e 1 , 0 0 0 , 0 0 0 t h v i s i t o r .
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F i g . 5 6 . 4 . P a t Howard d e f e n d i n g h i s t h e s i s d u r i n g t h e symposium a t L a s Vegas, C a e s a r s ' P a l a c e , on December 2 , 1971. S t a n d i n g : P.Y. Howard, s e a t e d : J . O r o , E. Gil-Av, W.E. Wentworth, J . L . Bear, W . P a r r , A . Z l a t k i s , and B. H a l p e r n . O t h e r symposia h a v e been h e l d i n T o r o n t o , Munich and Amsterdam. The l a t t e r had a r e c e p t i o n a t t h e Rijksmuseum amongst t h e Rembrandts, Vermeers and F r a n s H a l s ' . A p e r s o n a l t r i b u t e from some of my c o l l e a g u e s a t t h e Munich m e e t i n g w i l l always b e remembered. A s I l a t e r found o u t , t h e o r i g i n a l s c r o l l they had prepared w a s l o s t i n t h e o v e r s e a s m a i l and i t had t o b e r e p l a c e d a t t h e l a s t m i n u t e . Among t h e f o r e i g n s c i e n t i s t s who have c o n t r i b u t e d h e a v i l y t o t h e s u c c e s s o f t h e s e i n t e r n a t i o n a l symposia a r e V i c t o r P r e t o r i u s o f South A f r i c a , Denis D e s t y , Howard P u r n e l l , Tony James, C h a r l e s Brooks and John Knox o f t h e U n i t e d Kingdom, George Guiochon o f F r a n c e , E r n s t B a y e r , G e r h a r d Schomburg and Rudolf Kaiser o f Germany, J o s e f Huber of A u s t r i a and p a r t i c u l a r m e n t i o n s h o u l d b e made o f a "Hungarian q u a r t e t " : L e s l i e E t t r e (U.S.A.) I s t v h n H a l h s z (Germany), Csaba Horvkth (U.S.A.) and E r v i n KovP s ( S w i t z e r l a n d ) who are e s t a b l i s h e d i n v e s t i g a t o r s i n chromatography Many o f t h e s e h a v e been honored w i t h t h e T s w e t t Chromatography medal which w a s i n t r o d u c e d a t t h e 1974 Symposium i n Houston. The r e n n a i s s a n c e o f l i q u i d chromatography i n 1966 h a s b r o u g h t many o f t h e g a s chromatography s p e c i a l i s t s i n t o new f r o n t i e r s . Among o t h e r s , D r s . H a l i s z , H o r v h t h , Knox, K i r k l a n d , Huber and S c o t t have made t h i s t r a n s i t i o n e f f o r t l e s s l y . I t now a p p e a r s t h a t t h i n - l a y e r chromatography w i l l a l s o h a v e a s e c o n d g e n e r a t i o n of r e s e a r c h and development. T h e r e i s p r o b a b l y no one i n d i v i d u a l who i n f l u e n c e d t h e c o u r s e o f my career more t h a n t h e E n g l i s h s c i e n t i s t J i m Lovelock. My f i r s t a w a r e n e s s o f t h i s g e n t l e man w a s t h r o u g h h i s p a p e r on t h e a r g o n i o n i z a t i o n d e t e c t o r which w a s p u b l i s h e d i n t h e f i r s t i s s u e o f t h e Jouu*na2 of Chromatography i n 1958. I n t h e f a l l of t h a t y e a r I l e a r n e d
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Fig. 56.5. Las Vegas, 1966. A. Zlatkis and E. Bayer at the tourist bureau. that he was planning to spend some time in Dr. Lipsky's laboratory at Yale. Shortly after his arrival in the U.S.A. I called New Haven and asked him to visit me in Houston. I was pleasantly surprised when he accepted and it was only much later that I learned that Jim has always had difficulty refusing invitations by telephone. We spent an exciting week working to assemble a capillary chromatographic system and then published the first American paper on this subject (3). This was the beginning of a long personal and professional relationship with Jim Lovelock, much of our collaboration involving ionization detectors. In 1975 Jim was awarded a Tswett Medal for his outstanding contributions to chromatography. Special mention should be made of Professor A.J.P. Martin whose genius has been responsible for the direction of many careers. He has made profound contributions to all fields of chemistry over the past 45 years. His work has ranged from research in vitamin deficiencies, factors controlling insulin secretion and the production of penicillin to the development of liquid partition chromatography, the invention of paper chromatography, the development of displacement electrophoresis and above all the invention of gas chromatography. If one considers the problems scientists would face working in the field of chemistry without the techniques of paper chromatography, liquid partition chromatography, and gas chromatography, one begins to realize the tremendous impact of this man's work in science today. Very few laboratories indeed do not possess the gas chromatograph, an instrument which is an ever present monument to Dr. Martin's innovative achievements and scientific contributions.
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F i g . 56.6. Symposium a t Houston, O c t o b e r 30, 1976. S t a n d i n g ( l e f t - t o - r i g h t ) U t e H e z e l , C . M e r r i t t , C. G u i l l e m i n , M . J . E . Golay, G . D i j k s t r a , R.E. Sievers. Seated: Esther Zlatkis, A. Zlatkis. Although a volume c o u l d be w r i t t e n p e r t a i n i n g t o my p e r s o n a l r e m i n i s c e n c e s of D r . Archer M a r t i n , one i n c i d e n t may b e o f i n t e r e s t . A f t e r c o n v i n c i n g him t o j o i n t h e U n i v e r s i t y o f Houston i n 1974, a f o r m a l i t y o f o b t a i n i n g a l i s t o f h i s p u b l i c a t i o n s w a s r e q u i r e d . When I v i s i t e d Archer a t Abbotsbury - a medieval c a s t l e i n London, - I asked him f o r t h i s l i s t . S i n c e one d i d n o t e x i s t h e s u g g e s t e d he c o u l d s u p p l y some of t h e r e p r i n t s . An a n c i e n t c a b i n e t d i s c l o s e d a l a r g e number o f unopened packages c o n t a i n i n g r e p r i n t s i n c l u d i n g h i s f i r s t p u b l i c a t i o n i n 1931 e n t i t l e d "On a New Method o f D e t e c t i n g P y r o e l e c t r i c i t y " . I c o l l e c t e d t h e n e c e s s a r y r e p r i n t s and w a s a b l e t o assemble t h e r e q u i r e d l i s t . I t may b e o f i n t e r e s t t o n o t e t h a t h i s n i n t h p a p e r p u b l i s h e d i n 1941 on p a r t i t i o n chromatography a t t h e age o f 30 paved t h e way f o r h i s Nobel P r i z e . Twenty y e a r s have p a s s e d s i n c e my f i r s t chromatography p a p e r and d u r i n g t h i s t i m e my e f f o r t s have been d i r e c t e d i n t o some f a i r l y d i v e r s e areas. These i n c l u d e c a p i l l a r y columns, i o n i z a t i o n d e t e c t o r s , flow programming, a n a l y s i s o f lunar m a t e r i a l s , and f l a v o r c o n s t i t u e n t s o f c o f f e e , c h e e s e s and mushrooms. I n r e c e n t y e a r s t h e environment and b i o l o g i c a l f l u i d s have a t t r a c t e d o u r a t t e n t i o n . N e w t e c h n i q u e s have been developed f o r t h e c o n c e n t r a t i o n o f o r g a n i c v o l a t i l e s by u s i n g a hydrophobic porous polymer Tenax ( 2 , g - d i p h e n y l polyphenylene o x i d e ) ( 4 ) . The a n a l y s i s of t r a c e o r g a n i c c o n s t i t u e n t s ( 5 , 6 ) i n a i r ,
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Fig. 56.7. At the University of Houston, in 1961: J.E. Lovelock and A . Zlatkis examining new ionization detector designs.
Fig. 56.8. Presentation of the Tswett Chromatography Medal to J.E. Lovelock at Munich, November 3, 1975. L.S. Ettre, A. Zlatkis and J.E. Lovelock.
482 water, u r i n e , serum, s a l i v a and c e r e b r o s p i n a l f l u i d are now r e a d i l y o b t a i n e d . I n c o l l a b o r a t i o n w i t h D r . Hartmut L i e b i c h o f Tubingen, Germany, w e have b e e n a b l e t o d e t e r m i n e a number o f s i g n i f i c a n t m e t a b o l i t e s which a r e i m p o r t a n t i n t h e d i a g n o s i s o f diabetes m e l l i t u s M e t a b o l i c p r o f i l e s are p r e s e n t l y b e i n g d e v e l o p e d f o r s e v e r a l o t h e r diseases ( 7 ) . These y e a r s h a v e been most e v e n t f u l and e x c i t i n g , y i e l d i n g many f r i e n d s h i p s from a l l p a r t s o f t h e g l o b e . I n p a r t i c u l a r , my c o l l a b o r a t i o n w i t h L e s l i e E t t r e , o u r r e s i d e n t h i s t o r i a n o f chromatography, i n e d i t i n g many books and o r g a n i z i n g t h e i n t e r n a t i o n a l symposia h a s i n d e e d been a r e w a r d i n g o n e . REFERENCES 1 A . Z l a t k i s , B. Zak and A . J . Boyle, J. Lab. CZin. Med. 4 1 (1953) 486. 2 A . Z l a t k i s , Anal. Chem. 30 (1958) 332. 3 A . Z l a t k i s and J . E . Lovelock, Anal. Chem. 31 (1959) 620. 4 A . Z l a t k i s , H . A . L i c h t e n s t e i n and A . T i s h b e e , Chromatographia 6 (1973) 6 7 . 5 K . Y . L e e , D. Nurok and A . Z l a t k i s , J. Chromatogr. 158 (1978) 377 6 G . H o l z e r , H . S h a n f i e l d , A . Z l a t k i s , W. B e r t s c h , P . J u a r e z , H. Mayfield and H.M. L i e b i c h , J. Chromatogr. 1 4 2 (1977) 755. 7 H . M . L i e b i c h , O . A l - B a b b i l i , A . Z l a t k i s and K . K i m , CZin. Chem. 212 (1975) 294.