THE CHEMICAL WORLD THIS WEEK
Edwin J. Cohn of Harvard Medical School demonstrated his n e v method for collecting and processing human blood before National Academy of Sciences C&EN REPORTS: National Academy of Sciences
Redox Reactions N o w Possible O n Electron-Exchange Resins Lighter, more simple equipment processes human blood continuously N E W HAVEN.-A new family of polymers, based on hydroquinone, will* exchange electrons with their environment and can be used to conduct oxidation and reduction reactions by the same methods employed with the familiar ion-exchange resins according to a paper presented here by Harold G. Cassidy of Yale University. Speaking before the annual fall meeting of the National Academy of Sciences, Cassidy pointed out that proton exchangers have been in commercial use for some time and it is surprising that no one had previously thought of the possibility of producing polymers wbich would release or absorb electrons. The simple requirement of the polymer is that it have a substituent group which is readily accessible and which can be reversibly oxidized under a wide range of conditions. Cassidy chose to use the quinone-hydroquinone system because this reaction had already been the subject of intensive study, the oxidation was known to be truly reversible, and the compounds were suitable for a wide range of chemical manipulations. 4942
To make the polymer, a vinyl group was substituted into t h e hydroquinone. Since the hydroxyl groups inhibited the polymerization of the vinyl hydroquinone they were masked off by esterifying with benzoic acid. After tbis treatment the polymerization proceeded quite easily to produce molecules with a molecular weight range between 50,000 and 60,000. The benzoyl groups were subsequently removed
The Week's Events Gilman Receives Midwest Award NPA's Chemical Group Headed by Klipsiein and Tracy . . . . Raw Material Supply for Paint Improves Conflict Over Synthetic Liquid Fuels Aired Factors Affecting Chemists' Salaries Studied Pennsalt Exchanges Common Stock with Sharpies Uses of Radioactive Wastes Surveyed
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by saponification to yield the electron-exchange resin. Additional investigation proved that copolymers with styrene or vinyl pyridine conld be produced with equal ease. Crosslinked polymers, which were insoluble in all solvents but glacial acetic acid were also produced in which the full exchange capacity of the individual chains was retained. Cassidy characterized his new resins as a sort of organic Jones reductor, which has the added advantage of conducting oxidation or reduction reaction without introducing any contaminant into the product. The industrial value of such a unit is obvious. Some immediate theoretical applications are apparent also. Enzyme chemists are interested in applying its mild conditions arid lack of contamination to studies of their systems. Other biocnemists have suggested that films of the polymer may afford valuable models for studying the effect of redox potentials on tHe passage of fluids through membranes and the driving forces involved in fluid transport. Blood Processing Simplified Just one year ago at the NAS meeting, Edwin J. Cohn of Harvard demonstrated t b e first mobile unit for the processing of freshly gathered human blood. At the most recent meeting Cohn described an essentially new procedure for processing blood which can be used in even lighter, less complex equipment and produces blood fractions that in some cases are superior to those previously obtained. The new procedure is continuous and processes the blood at the same rate that it is drawn from the donor. The collecting bottle has been completely eliminated. Cup centrifugation for the separation of cells has been replaced by a specially designed, low speed, continuous centrifuge. Refrigeration is now accomplished in heatexchangers and the subzero ethanol-water system has been replaced b y an aqueous system. The older separation technique used classical electrochemical reactions. These have now been superceded by specific interactions of the blood constituents with metals and sugars which are believed to approximate the reactions of the blood chemistry in the body. In using the new equipment the blood from the donor passes directly to an ionexchange resin chamber where the calcium and the platelets are removed. It is then cooled in a heat exchanger and centrifuged to remove the red and the white cells as separate fractions. The isoglutinins are removed from the centrifugate by treatment with stroma recovered from the red cells and the prothrombin is adsorbed out on barium sulfate. Zinc glycine is added to precipitate the plasma globulins AND
ENGINEERING
NEWS
Outstanding physical and chemical characteristics of N a l c o ion exchange materials provide excellent opportunities for development of new processing uses—as w e l l as for maximum utilization o f conventional ion exchange techniques. H e r e are quick facts o n three o f the N a l c o i o n exchange materials:
Nalcite
HCR
CATION EXCHANGE RESIN Styrene type cation exchange resin for fast efficient removal o f metal ions from water and a w i d e variety o f process liquids. Either salt or acid regeneration. H i g h operating capacity ( U p to 32,000 grains per cubic foot) w i t h n o capacity loss at h i g h temperatures (Up t o 2 5 0 ° F) o r over the entire p H range.
Nalcite
SAR
STRONGLY BASIC A N I O N EXCHANGE RESIN For substantially c o m p l e t e removal o f all acid-radical constituents from w a t e r and processing liquids. Operates efficiently o v e r a w i d e pH range (2.0 t o 10). Microspheres o f uniform size range.
Naicite
WBR
WEAKLY BASIC A N I O N EXCHANGE RESIN A n e w p o l y s t y r e n e - p o l y a m i n e type anion exchanger of h i g h chemical stability. H i g h capacity for removal o f the stronger acids makes Nalcite W B R particularly applicable for demineralization techniques. Supplied i n bead form. N A T I O N A L ALUMINATE CORPORATION 6199 West 66th Place Chicago 38, Illinois Canadian inquiries should be addressed to Alcbem Limited, Burlington, Ontario, Canada
P R O D U C T S • · · S e r v i n g Indiislry iiiromgh Practical Applied Science VOLUME
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THE CHEMICAL WORLD THIS WEEK which are removed b y centrifugation, a n d the residual zinc is eliminated b y another ion-exchange column. T h e product is filled directly into t h e sterile plastic bottle in which it will b e distributed. T h e product is called stable plasma protein solution a n d differs from t h e plasma previously o b tained in that i t is mostly pure albumin while the earlier product contained several minor coir>~>onents. T h e SPPS appears from preliminary tests to b e as stable as pure albumin a n d should replace serum albumin and b o t h w e t and dry plasma for stockpiling purposes, according to Cohn. Slight modification of t h e equipment makes it suitable for the recovery of stable proteins from outdated whole blood. It also can be used for analyzing whole blood. T h e possibility of outside contamination is completely eliminated because the processing system is completely sealed from the donor's vein to t h e shipping container.
teron bombardment. At room temperature the effective cross section of t h e molecule for deuteron absorption equals a/bout half the actual size assuming that the enzyme has a molecular weight of at>out 250,000. The effective cross section retains this dimension until «the sample i s heated to 316° K. Above this temperature through d range of 2° the effective cross section increases through a range of 2° a n d then holds its n e w plateau until 377° K . where it increases again through a %° range and then remains constant with the effective cross section essentially equal to the true cross section. This work w a s reported by R. B . Setlow of Yale. Other Yale investigators represented by Ernest Pollard bomharded t h e enzyme invertase. They found a temperature dependence that increased the effective cross section steadily from 9 0 ° K . to 200° K. From 200° K. to 320° K. t h e cross section remains fairly constant at a value a p proximately that of the true cross section but above that temperature the effective
area increased rapidly indicating, according to Pollard, t h e formation of a highly sensitive condition i n t h e enzyme. T h e factor responsible for transformations in pneumococci also c a n b e inactiv a t e d u n d e r ionizing radiation a n d its sensitivity also has a thermal dependence, according to another group of investigators reporting from Yale and Brookhaven National Laboratory. This dependence was not completely delineated b y t h e speaker, D o n a l d J . Fluke. All of t h e speakers agreed that t h e temperature d e pendence could be explained in terms of energy migration within t h e extremely large enzyme molecules. At low t e m p e r a tures the energy released b y a primary ionization cannot spread through t h e molecule. However, above some threshold temperature t h e electrons attain full m o bility within t h e molecule a n d energy i n troduced at o n e point is carried t o t h e entire structure. T h e sensitized state discovered in invertase is less easily explained and will b e t h e subject of further studies.
Glucuronic Acid T h e exponents of the use of glucuronic acid as a therapeutic agent suffered a setback from t h e report of investigations of C. Glenn King of Columbia University and hi.s associates w h o found b y feeding C u tagged glucuronic acid to experimental animals that almost 9 5 % of the acid is decomposed a n d respirated within a short time after ingestion. Most of t h e rest of C & E N REPORTS: Midwest A w a r d the tagged carbon can be accounted for in conjugated compounds that appear in ST. LOUIS.—The seventh a n n u a l presentions at a testimonial b a n q u e t here Nov. 5. t h e urine. King inferred from this that tation of the Midwest Award, established In presenting t h e medal to Dr. Gilman, very little of t h e material finds its way by the St. Louis Section of the AMEEUCAN section chairman Joseph R. D a r b y of into the body tissues beyond the liver. C H E M I C A L SOCIETY t o give public r e c o g Monsanto Chemical C o . praised particuKing also reported that when glucose nition t o outstanding accomplishments in larly the unusual latitude of Dr. Gilman's 14 uniformly t a g g e d with C is fed to rats chemistry in the Mi&wesc area, has been research undertakings in varied chemical o r guinea pigs t h e biologically synthesized conferred upon Henry Gilman of the Iowa fields. Since most chemists find it possible ascorbic a n d glucuronic acid seems to State College o f Mechanical Arts. T h e to investigate only narrow fields of chemh a v e the same distribution of heavy caraward, a gold medallion, was presented istry within a lifetime, said Mr. D a r b y , b o n as t h e glucose. However, when the to Dr. Oilman f o r his chemical contribuit is rare to find such a m a n as H e n r y glucose is tagged with the heavy isotope in t h e one position some of t h e body-formed Henry Gilman of Io-wa State College receives the 1951 Midwest A w a r d medallion acids have t h e carbon isotope in t h e midfrom St. Louis Section C h a i r m a n Joseph R. D a r b y of Monsanto C h e m i c a l C o . d l e of t h e chain. King theorized that this phenomenon must indicate either that the glucose chain is broken in the middle a n d reformed in t h e acid synthesis or that t h e glucose is oxidized from t h e ends and completely rearranged to form ascorbic acid. Further experiments with feeding glucuronic acid a n d borneol, a toxic substance, to t h e experimental animals proved conclusively for t h e first time that t h e glucuronic acid will act as a detoxifying agent. C14 tagging showed that about two thirds of t h e borneol excreted was combined with the preformed glucuronic acid that w a s fed to t h e animals. T h e remaining one-third w a s excreted as a glucuronic acid conjugate b u t t h e position of the tagged carbon indicated that the acid h a d been formed in t h e body. Enzymes a n d certain other body catalysts may b e inactivated b y ionizing radiation a n d this inactivation effect is temperature d e p e n d e n t , according to several papers p r e s e n t e d at t h e meeting. Catalase, for instance, losses its ability to d e compose hydrogen peroxide u n d e r d e u -
St. Louis Section Honors Gilman as Recipient- of 1951 Midwest A w a r d
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