124th NATIONAL ACS MEETING characteristics. Robert F. Serro and Robert J. Brown of G r e a t W e s t e r n Sugar Co. have devised a simplified quantitative chromatographic m e t h o d for determination of raffinose in raw sugar beet juices a n d other processing liquors a n d a m e t h o d for quantitative d e t e r m i n a t i o n of inositol a n d galactinol, recently demonstrated by t h e authors to occur in beet juices.
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Improved Yields of D e x t r a n
Researchers working at t h e Northern Regional Research L a b o r a t o r y u n d e r t h e direction of C. E. Rist r e p o r t e d improved methods for t h e p a r t i a l hydrolysis and s u b s e q u e n t fractionation of dextran N R R L B512 that make p o s s i b l e yields of clinical size dextran ( w e i g h t a v e r a g e molecular weight, 75,000 i t 2 5 , 0 0 0 ) u p to 4 7 % , more than twice previously realized yields. In t h e production of clinical dextran, used as a blood plasma extender, careful control of the hydrolysis is t h e most important factor in achieving h i g h yields of dextran to meet t h e exacting molecular weight specifications. Molecular weight determinations are m a d e b y light scattering; improvements in these t e c h n i q u e s include methods for t h e p r e p a r a t i o n of samples of highest purity and a modification of t h e light scattering p r o c e d u r e to eliminate adsorption of dextran b y the porcelain filter candles that a r e u s e d to clarify t h e samples. N R R L workers h a v e prepared six different dextrans from strains of Leuconostoc mesenteroides. Surveys of m o r e microorganisms m a y reveal an unlimited n u m b e r of new dextrans t h a t c a n b e tailor-made to specifications for p a r t i c u l a r industrial use. Information r e g a r d i n g t h e molecular heterogeneity of such d e x t r a n s is a major concern in use studies.
DIVISION OF CHEMICAL EDUCATION
Chemists' V i e w s Should Prevail in Inferior Design of Chem Buildings • Advances in large rings, free radical reactions, and stereochemistry highlight organic symposium ^ Prediction of properties of elements 99 to 103 possible by comparison of their rare earth homoiogs ^ Instruction in organic analysis is not keeping pace as to length and type with industry's needs
T ET architects design exteriors of new -*-* chemistry buildings, b u t let t h e chemists' views prevail as to interior design— this is one of the major conclusions r e a c h e d b y several educational institutions which have recently faced this problem. A symposium on the do's and don't's of chemistry b u i l d i n g construction, given by t h e Division of Chemical Education, b r o u g h t forth a host of problems involved in this area. Zooming construction costs h a v e focused considerable attention on such details as careful design to assure maximum effective utilization of space and critical evaluation of actual needs for certain types of e q u i p m e n t a n d services. O n e way to assure that t h e chemists get their views across is to h a v e one m e m b e r of the chemistry staff assigned the responsibility of representing t h e d e p a r t m e n t in all stages of p l a n n i n g a n d construction. Seven participants in t h e symposium have all been engaged in recent construction programs on their campuses. I n addition t o t h e symposium chairman, A. H. E l b e r t G. Smith, University of H a w a i i , Kunz, University of Oregon, other symbecomes 1000th m e m b e r of Division of posium speakers were George H . FlemC h e m i c a l E d u c a t i o n a n d is c o n g r a t u l a t e d b y t h e treasurer of t h e division, F r e d ing, Pennsylvania State College; Earl M. B . D u t t o n , from M i c h i g a n State College Bilger, University of Hawaii; Ray Q. Brewster, University of Kansas; G. K. Rollefson, University of California ( B e r k e l e y ) ; M. G. Mellon, P u r d u e University; and G. Ross Robertson, University of California ( Los Angeles). In addition to the p r o b l e m of convincing architects that chemists h a v e good reasons for setting forth certain requirements, a t r e m e n d o u s n u m b e r of major and minor problems were e n c o u n t e r e d at every stage from p l a n n i n g to final construction. O n e trend w h i c h appears to b e developing is the practice of sharing a building with other d e p a r t m e n t s such as biology, physics and pharmacy. In one case ( U C L A ) , this permitted separation of lecture halls from the laboratory building. In other cases, a separation of laboratories from offices a n d lecture rooms was effected within the laboratory building. Technical ideas expressed w e r e : need to place storeroom in central location; careful design of u n d e r g r a d u a t e and g r a d u a t e
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laboratories to prevent over-crowding; avoidance of unnecessarily elaborate plumbing, electrical, gas, oxygen, hydrogen sulfide, a n d various other service systems; accessibility of such lines for servicing; safety e q u i p m e n t ; provision of storage space, loading platform, freight and personnel elevators, lecture rooms, rooms for glass blowing, shop work, constant temperature studies and radioactive material work.
• Organic Symposium Among the recent a d v a n c e s in organic chemistry is progress m a d e in studies on large rings, Arthur C. C o p e , Massachusetts Institute of Technology told the symposium on recent advances in organic chemistry. He stated that he has f o u n d evidence that the spatial proximity of atoms o n opposite sides of rings containing eight, nine and 10 carbon atoms influences physical and chemical properties of such compounds. He also observed that among recent "transannular reactions" is t h e addition reaction of an olefin leading to a product in which the adding groups a r e not attached to the carbons originally united by a double bond. Other studies, h e pointed out, showed t h a t the eight-member ring is the smallest ring size k n o w n to accommodate a trans-ethylenic or acetylenic linkage. T o practicing organic chemists, steric, rather t h a n polar effects, a r e of major importance in m a n y organic reactions. H . C. Brown, P u r d u e University, said that while polar substituents may alter reaction rates by a factor of five or 10, steric effects may have a factor of a million or more. For this reason he said, inore attention should b e paid to steric effects t h a n is generally given in the study of organic theory. Determination of the absolute configuration of sodium rubidium t a r t r a t e by means of Ka rays is one of t h e five major recent advances in t h e stereochemistry of organic compnimrk J")nn:il(l J. C!rnm. University of California (Los Angeles) reported. Others include the correlation and prediction of the chemistry of six-member ring c o m p o u n d s containing asymmetric
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CHEMICAL
Chemistry building at Penn State College has several interesting design features including lead-clad steel ducts, each supplying four hoods, with clean-out plates on e n d and exhaust fans. Unistrut channels on walls allow use of adjustable shelves. Plumbing a n d electrical outlets appearing on floor will be inside laboratory benches centers by means of application of the concept of conformational analysis and demonstration of the existence of bridged ion pairs through consideration of stereochemical concepts. Steric concepts were applied to correlating differences of reactivity with structure in diastereomerically related acyclic systems. T h e fifth, Dr. Cram said, is the concept of steric control of asymmetric induction used to correlate and predict the course of reactions in which one asymmetric carbon is created in the presence of another. T h e majority of organic reactions which proceed through free radical intermediates show certain common characteristics, Chevcs Walling, Columbia University, reported. These are insensitivity to acid or base catalysis or change in polar properties of the medium and pronounced acceleration by light or peroxides and retardation by certain characteristic inhibitors. From his studies, D r . Walling has been able to classify free radical reactions into six types: radical producing, displacement, addition, rearrangement, decomposition, coupling and disproportionation. T h e rate and course of a radical reaction, he said, are dependent on resonance, stabilization of radicals, steric hindrance, and polar effects.
Dr. Seaborg said that the same principles may be applied to such elements as 104, 105. and 106 by comparisons with their homologs, hafnium, tantalum, a n d tungsten. Because these elements, 99 and above will have short half lives, they will have to b e identified by nuclear means, such as alpha particle emission, rather than chemical means. W i t h respect to inorganic polymerizations, L. F. Audrieth, University of Illinois, has been able to group these reactions into four categories. These a r e : condensation polymerization in solution and in the a b sence of a solvent, molecular polymerization, and disproportionation polymerization. Experiments with radioactive materials have been one means b y which differences between complexes, which differ in stability, can b e placed in one of two classes. John C. Bailar, University of Illinois, said that this technique helps determine whether a complex is in equilibrium with the metal ion and t h e coordinating agent. Further light has been shed on the structure of complexes b y the theory of "inner orbital" and "outer orbital" complexes. This recent knowledge will b e of practical value in treatment of water, deactivation of trace elements of undesired metals, and in dye chemistry. ^Organic
• E l e m e n t s 9 9 t o 103 Prediction of properties of elements 99 to 103 is possible by comparison with their five rare earth homologs, holmium to lutecium, respectively, and b y evidence obtained in ion exchange studies, Glenn T. Scaborg, University of California, reported to the symposium o n recent advances in inorganic chemistry. V O L U M E
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Instruction
Although t h e need for organic analysts has been increasing continuously for the past 10 t o 20 years, instruction in this subject in colleges has been inadequate both with respect to length of instruction and types of analytical procedures taught, according to James S. Fritz, Iowa State College. Speaking before the symposium on recent advances in analytical chemistry,
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1953
EDUCATION
he went on to describe three noteworthy trends in recent advances in quantitative organic analysis. These are the wide use of ultraviolet and infrared spectrophotometry, increasing use of functional group analysis, a n d development of methods for titrating organic acids and bases in nonaqueous solvents. In the theoretical treatment of analytical problems, too much reliance is placed on the law of chemical equilibrium, Donald D. D e F o r d , Northwestern University, stated. Neglect of activity coefficients, a n d neglect of so-called secondary equilibria can lead to significant errors. Consideration of ail equilibrium factors, particularly wrien secondary equilibrium constants are not known, is difficult and complex. In quantitative analyses the treatment of determinate errors is well established and grows from fundamental chemical principles. Indeterminate errors are less well recognized possibly because their fundamentals are more mathematical and statistical. In discussing this subject, Ralph A. Johnson, University of Illinois, said that application of classical statistics is difficult because t h e large groups of data needed are not available. By so-called modern statistics, he said, a method becomes available which is applicable to study of indeterminate errors in quantitative analysis. T h e principles may be applied to balances and to analytical methods. Faulty equipment, facilities, chemicals, unknowns, and erroneous or inadequate instructions lead to errors by students which are beyond their control. Indications of such instructional errors are noted in results obtained by most good students. Because determination of instructional error is troublesome and time-consuming for the instructor, W . J. Blaedel, University of Wisconsin, has set u p a system of control charts on experimental work. These are maintained by t h e students. The system helps the student a n d instructor in interpreting results and discovering errors. Teaching Problems. One teaching technique was reported b y William E . Morrell, University of Illinois, who said that h e has initiated a program of giving bonus points to students w h o find errors in textbooks. T h e program is designed to foster a scientific attitude a n d careful study of textbook material. Objections to traditional m e t h o d s of presenting reactions to beginners as taking place between atoms only and of considering molecules as composed of atoms were expressed by Alexander Gero, Hahnemann Medical College. D r . Gero favored emphasis on electron shells and their stability. W . P. Cortelyou, Roosevelt College, suggested that numerical grades be translated into letter grades through application of a simple statistical method based on deviation from a mean. He also noted that such a system could be applied to grading qualitative and quantitative analytical reports, as it woidd make allow3855
124th N A T I O N A L ACS MEETING anccs for differences in difficulties of de tecting certain ions. One way to give general science classes a better appreciation of the complex in terrelationships between research and de velopment in various related fields is to trace t h e development of typical materials. Stanley C. Bunce, Rensselaer Polytechnic Institute, has found this to he true with respect to synthetic detergents. Various oxidation states of an element at different ρ Η values can be put on clear film and projected in a slide projec tor. H . E. Bent, University of Missouri, proposed this idea as substitute for the costly three-dimensional models used in demonstration of dependence of a redox potential on concentration and p H . The film, however, does not give t h e entire picture at a glance. Another proposal for showing various stages of a reaction was discussed by Guido H. D a u b , University of New Mexico. He proposed that various stages of an organic reaction b e p u t on a series of cards. W h e n they are flipped rapidly, a simple motion picture of the reaction ap pears. Equipment. Minor alteration of Army surplus frequency meters makes possible their use as heterodyne-type dielectric constant apparatus, H. Bradford Thomp son, Michigan State College, reported. Several types of analytical experiments may b e carried out using simple easilybuilt crystal oscillators, James L. Hall. West Virginia University said. Typical applications are conductimetric titrations and determination of dielectric constants of liquids. Freedom from problems asso ciated with maintenance of metal elec trodes in solutions is avoided by this equip ment. A color and sound film is being used by David A. Fletcher at the University of Redlands to describe the theory, use. and laws governing visual and photoelec tric colorimeters, nephelometers, and fluormeters* T h e film, which runs 20 minutes, contains considerable animation. The ob ject is to familiarize students with types of equipment used in industrial and clini cal laboratories. College Ratings. An evaluation of col leges on the basis of the percentage of their chemistry baccalaureates who get their doctorates was reported b y B. R. Siebring, Wisconsin State College. Dr. Siebring's results differ from similar studies made in the past because he has compared doctorates attained in chemistry with bachelor's degrees granted only in the field of chemistry. Other studies have compared Ph.D.'s in chemistry with all A.B.'s granted by a college. The first 10 institutions according to this study are: Rice Institute, University of Idaho, California Institute of Tech nology, Notre Dame, Calvin College. Swarthmore, Massachusetts Institute Of Technology, St. Olaf College, De Fauw University, and Oberlin College. 3856
DIVISION OF CHEMICAL MARKETING AND ECONOMICS
Drug Product Research Speeded Up As Competition Becomes Intense ^ Drive for n e w m e d i c i n a l a g e n t s now costing industry a n d g o v e r n m e n t a b o u t $ 1 0 0 million a y e a r ^ C o m p l e x i t y increased for r e t a i l e r as e t h i c a l products a l o n e e m b r a c e 8 5 0 0 different items TNTENSIFIED competition within the phar•*· maceutical industry is making ever-in creasing demands on research and devel opment personnel, Leon A. Sweet, vice president of Parke, Davis and Co., told the symposium on market research and devel opment of pharmaceuticals and antibiotics, presented by the Division of Chemical Marketing and Economics. This discour ages mere copying, the speaker said, but places it greater premium on speed than on thoroughness and may result in the intro duction of new agents before they have heen adequately evaluated. T h e research program of a pharmaceuti cal organization must be geared to its own particular fields of interest, whether they he medical, dental, or veterinary, and must lake into account such factors as promotion methods, sales potential, and overseas out lets. The relative emphasis to b e placed on longer term research—the search for new drugs—and on shorter term r e s e a r c h product development—constitutes an im portant decision. T h e last two decades have brought sweeping changes within the pharmaceu tical industry, h e said. From accelerated research programs have come synthetic vitamins a n d hormones, sulfa drugs, anti histamines, and antibiotics. Increased pub lic interest in medical research, as evi denced by the funds for the study of specific diseases, together with more ex tensive federal support, promised to pro vide a broader product base for the indus try and to contribute materially to its con tinued expansion. T h e productivity of the pharmaceutical and antibiotics industry makes it increas ingly important to establish a new prod uct's brand position quickly, said John E. MeKeen, president ot Chus. Pfizer & Co. Mr. MeKeen, chairman of the symposium, stated that the cost ol such action is high. Detailing, advertising addressed to the professions, and public relations programs, must all b e used with great skill. Blun ders are incredibly costly. Still, there are research areas which offer further oppor tunities tor growth, such as the increase in the population of people older than 65. The whole spectrum of illness which physi cians are called upon to treat is shifting. \ e \ v therapeutic agents are needed for CHEMICAL
the treatment of h e a r t disease, arterio sclerosis, and hypertension; tuberculosis re mains a world-wide p r o b l e m . |> C o s t of D e v e l o p m e n t The s u m of industrial, institutional, and government outlays in the search for new medicinal agents is well over $100 million annually, in the opinion of F. M. Hadley, Eli Lilly & Co. Since the discovery of the antibiotics, he said, which h a v e a d d e d about 500v to the ethical drug market, there h a s been an unprecendented, almost frantic expansion in industrial p h a r m a c e u tical research. Organic and physical c h e m istry, biochemistry, pharmacology, biology, radioactive research, each came in f o r its fair share. Quoting d r u g market authori ties, t h e speaker said t h a t one r e s u l t of this was confusion in t h a t trade and some misunderstanding. In some instances, it w o u l d appear that l a r g e research out lays are paying off largely in prestige rather t h a n in increasing company growth. The speaker said it w o u l d b e until inkable for some m a n a g e m e n t s to c u r t a i l re search programs. It could not b e gainsaid that research is the very lifeblood of growth; hence management's p r o b l e m is placed squarely in the laps of their mar keting colleagues. F . A. Soderberg ( l e f t ) , chairman of mar keting division, and H a l Johnson, secre tary-treasurer, are pleased with division membership as it approaches 1000 m a r k
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