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events partially permeable to the sodium salt." Höber draws the conclusion that the permeability to salts is small, but he regards it also as possible that the whole phenomenon may simulate superficial adsorption, and finally C. Neuberg understood from the description of the experiments that the cell is "throughout" permeable to hexose-di-phosphoric salts. Smedley, MacLean and Hofferts in 1924 expressed the opinion "that the hexosephosphate molecules are not able to pass through the wall of the yeast cell, but that glucose and phosphate molecules pass separately into the cell, and are there combined." This assertion might be regarded as an unconscious application of the proposition of Ruhland and Hoffman according to which the smaller the volume of the molecules, the faster is supposed to be their penetration into plant cells. In spite of the fact that this is contradicted by the rule of Overton, the assertion possesses a certain probability.

We must remember that the almost impossible detection of hexosephosphates in fermentations by means of yeast cells is in good harmony with the abundant formation of hexosephosphates by fermentations which are free of cells. The membrane of the cell is scarcely permeable to the synthease of Iwanow. In the case of uninjured yeast cells, there is in the outer medium only a very small quantity of hexose-di-phosphate, which might partially penetrate into the cell. If we henceforth assume, especially in accordance with the considerations and experiments of Witzemann, Gurchot and others, that also the membrane of the yeast cell represents a dynamic system which might be compared to a copperferrocyanide membrane, and therefore can be acted upon by intermittent coagulation and peptization, then the whole process will become readily intelligible.

The externally produced hexose-di-phosphates penetrate into the interior of the cell until a suitable salt concentration is reached which brings about the coagulation of the membrane. Through the fissures of this now "crystalline" membrane, uncombined sugar-which is typically non-diffusible-can now penetrate into the cell where it will be esterified by means of the synthease there present. The alteration (not fermentation) of the hexosephosphates into the "transportation form" of the sugar which takes place isochronously, and which is again subject to the direct splitting into the compounds of the 3-carbon chain, changes the internal concentration of the salts in such a manner that a repeptization takes

5 It is probably through an error that M. Schoen (Monogr. de l'Institut Pasteur, No. 3, p. 128: 1926) recently ascribed this suggestion to other authors.

6 W. Ruhland and E. Hoffman, Arch. wiss. Bot., 1, p. 1, (1925).

place, the influx of the sugar ceases, and the cycle may be started again."

The chief characteristic of the process would be, under these conditions, an intermittent coagulationpeptization of the membrane, as well as endeavoring to maintain a membrane equilibrium in the sense of Clowes (1916). No acceptance is expressed, herewith, of his or v. Möllendorff's (1918) opinion that the membrane is comparable to an emulsion, which, of course, would make it impossible to understand the osmotic activities of the cell.

It is probable to a high degree that the greater part of the sugars is esterified within the cells where the enzymes exerting fermentation are located and where they will be liberated. It is, therefore, very important to possess a conception of the mechanism of the admittance. In contrast to this, it is only of secondary significance as to whether the hexose-diphosphates originate through an intermediate hexosemono-phosphate (compare, for instance, Komatsu and Nodzu, 1924). In any case, they are disintegrated and leave behind the sugar in the transportation form, which is readily cleavable and which does not need to be re-esterified.8 Isochronous rearrangements of intermittent processes exclude, of course, the accumulation of any intermediate products in the case of a normal method of fermentation.

The chief characteristic of the transportation form of a compound or system may be regarded as its capability either to mediate in intermittent actions, or to enable irreversible reactions to proceed, especially in cases where the use of a potentially higher energy content is involved. It is not supposed to exist in a form which can be investigated successfully by means of our present tools as a chemical entity. Its capacity to promote the aforementioned types of biological reactions is probably due in the main to an electron transfer caused by the ionic antagonism within the cell. Ionic antagonism, we know, also exerts a great influence upon enzyme action and there are certain reasons for assuming that the same is also true for the influence of adsorption. The reasons why it is improbable that we deal in the latter case with "molecular compounds" in the sense of P. Pfeiffer will be presented in a later paper.

At this point of the considerations, attempts were made to ferment the readily accessible hydroxy-pyruvic aldehyde in its mono-molecular or trimeric form,

7 Compare G. Bredig and M. Minaeff, Festschrift Z. Hundertjf, d. Technischen Hochschule Karlsruhe, 1925. 8 O. Meyerhof, Die Naturw., 41, 757 (1926).

It is under these circumstances misleading when e.g., the hexose-mono-phosphoric acids are recently designated to be "active" (compare O. Meyerhof, Die Naturwissen schaften 14, 1179 (1926)).

with the purpose of obtaining a better insight into the processes governing the decomposition of the 3-carbon chain compounds. No significant fermentability of a 2 per cent. solution could be observed by means of the American top or bottom yeasts which were at my disposal, in the presence or absence of mono-potassium phosphate, not even after digestion for several days at 34° C. This observation does not justify at present the drawing of definite conclusions regarding the behavior of this compound toward yeasts especially in comparing its behavior with the simultaneously effected control fermentation of d-glucose.10 In any case the substances are not biological equiva

lents.

Under these conditions, we could be inclined to doubt11 the view of Neubauer concerning the occurrence as an intermediate product of pyruvic acid in the course of alcoholic fermentation which requires as a first step methylglyoxal. C. Neuberg, Hildesheimer and Karczag in 1911 reinvestigated this question on a macro-chemical scale and, after an uncertain interpretation in a brilliant manner confirmed the previous statement concerning the transient existence of this acid. Fortunately it does not seem necessary to question these observations when we take into consideration that the experiments of Neubauer or the last-named authors are not depending on each other, viewed from a biological standpoint. In contradiction to this, the assertion that pyruvic acid is acted upon faster by fermentation than is sugar could not be confirmed by the exact investigations of Lebedew (1917, 1924), Hägglund and Augustson (1925) and others, all the more, as the control experiments on the fermentability of the pyruvic acid were carried out under unphysiological conditions. The authentic measurements of the absorption spectra by Henri and Fromageot, to which we referred already in 1925, show that under conditions of biochemically permissible concentrations, the acid is only present in the readily fermentable enol form. On the other hand, we know that the pyruvic acid is a very strong acid (K 0.56) and since it is so highly dissociated, in accordance with the observations of Brenner, 12, Brooks,13 and others,

=

10 This observation is in contrast to yet unpublished results obtained with Miss Mollie G. White, when this compound is acted upon by fusarium lini B. In this case it was possible to show that this fungus may utilize this compound as a sole carbon source.

11 Compare also H. v. Euler, Samml. chem. u. chem. techn. Vortr., 28, No. 6/7, p. 60 (1926).

12 W. Brenner, öfvers. Finska Vetensk.-Soc. Forhandl., 60, A, No. 4 (1917-1918).

13 M. M. Brooks, Public Health Reports, No. 845 (1923).

it may only enter uninjured cells or reach the place of enzymatic activity with great difficulty if at all. The connection of these observations is clear! The acid which is originated in a biochemical process, that is to say, within the cell, is present in the enol form which is readily fermentable. It will be isochronously decarboxylated with the same speed as the transportation form of the sugar is formed. In contra-distinction to this, when pyruvic acid is added to the mash itself, it is in an uncomparable degree more highly concentrated and will be fermented only in such proportion as the enol form is present and ready to undergo disintegration. This again is dependent on its ability to penetrate into the cell. We see, therefore, in conformity with earlier results first the outstanding significance of the transportation form of a compound which is indispensable to the initiation of a biochemical reaction.14 There belong probably in this small group also some sulfur containing compounds newly described and investigated which were supposed to have a decisive rôle in reversible physiological processes and certain compounds of the bile promoting the hydrodiffusion of the cell.15 The same importance also attaches to the "isochronic rearrangement" of this form, to which we referred recently16 in connection with certain It may, therefore, be regarded as certain that "unphysiologic" pyruvic acid is fermented slower than sugar in contra-distinction to the "biologic" acid which ferments practically with the same speed as sugar. It appears equally probable that considerations based on structural organic chemistry alone are hardly suitable to justify positive or negative conclusions which may be drawn from the macrochemical behavior of methylglyoxal, hydroxypyruvic aldehyde or related compounds concerning their behavior under biochemical conditions. Accordingly in the case of intracellular reactions there does not appear to be any logical basis for the calculation of a quotient based upon the rate of the fermentation of glucose as compared to that of pyruvic acid.

cases.

The more we increase our knowledge concerning the marvelous functions of the cell, the more we appear to be justified in explaining chemical reactions.

14 It does not seem desirable at present to complicate the conception by analyzing the highly probable influence that the transient acid must have on the interfacial tension of the membrane.

15 Edward C. Kendall and F. F. Nord, Journal Biol. Chem., 69, 295 (1926). F. F. Nord, Die Naturwissenschaften, 15, 356 (1927).

16 F. F. Nord, Germ. Patent No. 434728/120 (1924); F. F. Nord, Beitr. z. Physiologie, 2, 301 (1924); C. Endoh, Rec. trav. chim. 44, 866 (1925).

on the generalization of a concept of transportation forms in contra-distinction to forms of a compound which can only be described by formulas represented in the usual manner of structural chemistry. It would also be necessary, before we can wholly explain the reactivity of the transportation form as contrasted to the ordinary form in its relation to the various variables, to know the arrangement of the electrons within the compound and the rôle which the electrical forces17 play in the activity of the transportation form.

It is intended to report later in greater detail the experiments which are now in progress.

UNIVERSITY FARM,

ST. PAUL, MINNESOTA
November 30, 1926

F. F. NORD

PROTEUS HENRICENSIS NOV. SPEC.

A MICROORGANISM believed not to have been previously described has recently been isolated from putrefying material. The characteristics of this bacillus are such that it may be placed in the classification of Castellani and Chalmers, but not in the classification of Bergey, et al.

The genus Proteus Hauser1 is defined as "highly pleomorphic rods." Filamentous and curved rods are common as involution forms. Gram-negative. Actively motile, possessing peritrichous flagella. Produce characteristic amoeboid colonies on moist media and decompose proteins. Ferment dextrose and sucrose but not lactose. Do not produce acetylmethyl-carbinol.

The tribe Proteae Castellani and Chalmers, 1918,2 is defined as "Bacillaceae growing well on ordinary laboratory media, not forming endospores, aerobic, without fluorescence or pigmentation, but liquefying gelatin." The tribe may be divided into genera as follows:

(A) Rapid gelatin liquefaction; do not ferment lactose; mostly Gram positive—Proteus.

(B) Slow gelatin liquefaction; ferment lactose; Gram negative Cloaca.

The isolated microorganism has the following characteristics:

Rods: 0.5 to 0.7 by 1.0 to 3.0 microns, occurring singly and in pairs. Actively motile. Gram-negative. No spores.

17 Compare J. N. Mukherjee und B. N. Ghosh, J. Ind. Chem. Soc. 1, 213 (1924).

1 Bergey, et al., "Manual of Determinative Bacteriology," 1923, page 209.

2 Castellani and Chalmers, "Manual of Tropical Medicine," third edition, 1919, page 943.

Aerobic and facultative anaerobic.

Gelatin colonies: Irregular, spreading, rapidly liquefying.

Gelatin stab: Rapid, stratiform liquefaction. Agar colonies: Opaque, gray, spreading. Agar slant: Thin, bluish-gray, spreading. Broth: Great turbidity, with thin, bluish pellicle. Milk: Slightly acid, becoming markedly alkaline in forty-eight hours. Quick peptonization. Indol formation abundant. Acetyl-methyl-carbinol not formed. Nitrates not reduced.

HS formed. Lead acetate turned brown.

Acid and gas in dextrose, xylose, trehalose and galactose.

Acid in glycerol.

No acid or gas in lactose, sucrose, mannitol, dulcitol, raffinose, levulose, arabinose, inositol, maltose, dextrin, salicin or sorbitol.

Not pathogenic for guinea pigs or rabbits.

This organism appears to be closely related to Proteus diffluens Castellani, 1915. It differs from diffluens in that it peptonizes milk, produces indol and does not liquefy coagulated blood serum. No information is at hand as to the action of P. diffluens on xylose and trehalose.

The name Proteus henricensis is suggested.
FREDERICK W. SHAW

MEDICAL COLLEGE OF VIRGINIA,
RICHMOND

THE RELATION OF TEMPERATURE TO HYDROGEN-ION CONCENTRATION

OF BUFFER SOLUTIONS

THE influence of temperature on optimum hydrogen-ion concentration for diastatic activity of malt has been discussed by Olsen and Fine.1 The experimental evidence submitted showed that with "water suspensions of a mixture of wheat and malted barley flours . . . containing different amounts of dilute acid and alkali [HCl and NaOH were used] ... the optimum pH changes from about 4.3 at 25° C. to beyond 6.0 at 69° C." These authors "suggested that this change is due to the increased activity of the hydrogen-ions present and that these apparently different pH measurements would represent approximately equal hydrogen-ion activities if measured at the temperature of the reaction."

Similar observations have been made for other enzymes. More than thirty-five years ago O'Sullivan and Tompson2 observed for invertase that "the most

1 Olsen, Aksel G., and Morris S. Fine. Cereal Chem., Vol. I (1924), pp. 215–221.

2 O'Sullivan, C., and F. W. Tompson. Jour. Chem. Soc., Vol. 57 (1890), 834-931.

...

favorable amount of acid . . . decreases with rise in temperature," and Compton3 has pointed out that the optimum temperature for maltase "is dependent on the H+ concentration of the medium."

Recently Lüers and Nishimura have reported observations on the basis of which they conclude that Olsen and Fine were in error. These authors used a highly active amylase preparation and soluble starch in strong acetic acid-acetate buffer solutions and found no change in optimum pH as the temperature was raised from 15 to 70° C.

Lüers and Nishimura in drawing their conclusions failed to take into account that different buffer solutions respond differently to changes in temperature. McIntosh and Smart found the hydrogen-ion concentration of acetate buffers to remain constant between room temperature and 70° C., and Walbum later reported extensive measurements on a number of buffers. Some of these were found not to change in hydrogen-ion concentration as the temperature was raised from 10-70° C., while certain others changed markedly. The following figures are quoted from Walbum:

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Recent measurements by Hoffman and Gortner" have shown that the pH of dilute solutions of hydrochloric acid and sodium hydroxide also respond to changes in temperature.

Inasmuch as Lüers and Nishimura were making their determinations with acetate buffer mixtures which, according to McIntosh and Smart, do not change with change in temperature, their results not only harmonize with those of Olsen and Fine but tend to corroborate the suggestion that the observed differences were due to changes in the activity of the hydrogen-ions. The different results obtained in these two cases emphasize the importance of proper selection of buffer solution where the reactions occur at temperatures other than that at which the acidity is measured.

POSTUM COMPANY, INC.

AKSEL G. OLSEN

3 Compton, A. Proc. Royal Soc., Vol. 88B (1915), 408-417.

4 Lüers, H., and S. Nishimura. Woch. f. Brauerei, Vol. XLIII (1926), pp. 415-416.

5 McIntosh, J., and W. A. M. Smart. The Brit. J. Expt. Pathology, Vol. I, 1920) 9-30.

6 Walbum, L. E. Biochem. Zeitschrift. Vol. 107 (1920), 219-228.

7 Hoffman, Walter F., and R. A. Gortner. Colloid Symposium Monograph, Vol. II (1925), 262-269.

THE NATIONAL ACADEMY OF

SCIENCES

(Continued from page 454)

τ

.

Thermionic emission and the "universal constant"' A: EDWIN H. HALL. Richardson, in his "Emission of Electricity from Hot Bodies" (1916), has given three bo derivations of the equation I= ATε The first of these, beginning on page 28 and ending on page 33, has been much criticized. The third, running from page 35 to 39, follows the quantum theory and reaches a result, as to the value of A, not very different from that recently found by Dushman in a similar way. The seeond derivation, given on a single page, 33 to 34, is admirably simple and direct, but Richardson felt obliged to give it up, because of a misgiving as to assigning thermal energy to the free electrons within a metal, though this conception of their condition is a familiar and natural one. The purpose of the present paper is to show that such a misgiving lacks justification, and to restore, with some modifications, suggested by the dual theory of electric conduction, Richardson's "classical kinetic theory" of thermionic emission.

The minimum values of positive quadratic forms: H. F. BLICHFELDT, Stanford University. Having given a positive definite quadratic form in n variables, the important question as to the least numerical value of this form, expressed as a function of n and the determinant D of the form, the variables being allowed to take on only integral values (not all zero), has received a good deal of attention. The minimum in question is gD|1/n, where g is a function of n only. Superior limits to g were given by Hermite, Korkine and Zolotareff, Minkowski and the author. Exact limits are known for n=2, 3, 4, 5, to be 4/3, 2, 4, 8, respectively. In the present communication the author states that the exact limits for n=6, 7, 8 are 64/3, 64, 128, respectively.

Pressures in discharge tubes: W. H. CREW and E. 0. HULBERT, Naval Research Laboratory. The increase in the pressure of the gas in a discharge tube due to the discharge has been measured for those pressures normally used in discharge tubes, from about 0.1 to 30 mm of mercury, for helium, hydrogen, oxygen, nitrogen, air, carbon monoxide and carbon dioxide. The pressure increase is regarded as due to two chief causes, one, the increase in temperature of the gas, and the other, the dissociation of the molecules of the gas into atoms or less complex molecules. Therefore, from the observed pressure increments, the temperatures and the amounts of dissociation of the gas in the discharge have been determined. A long slim discharge tube, 300 cm in length and 9 mm in internal diameter, and a large tube, 80 cm in length and 34 mm in internal diameter, were used in turn. The pressures below 1 mm of mercury were measured by a striation gauge. This consisted of a second discharge tube (joined to the main tube) excited by direct current calibrated so that the shift of the striations of the positive column with pressure was known. The pressures from 3 to 30 mm of mer cury were measured by an oil manometer.

Current distribution in supra conductors: FRANCIS B. SILSBEE, Bureau of Standards. Some very clever experiments on the resistance of a tube of tin, when subjected to the magnetic field of currents both in the tube and also in a wire coaxial with it, have been described by Kamerlingh Onnes and Tuyn (Journal Franklin Institute, vol. 201, page 379, 1926). In the present paper the magnetic field distribution to be expected in such a system of conductors is analyzed in detail on the basis of a number of simplifying assumptions and the resulting potential gradient in the tube found to agree fairly well with the observed values. It therefore appears that the phenomena can be accounted for quantitatively by the assumption of a critical magnetic field and do not require the introduction of the concept of "critical current.''

Heats of condensation of positive ions and the mechanism of the mercury arc: K. T. COMPTON and C. C. VAN VOORHIS, Princeton University. The two most suggestive lines of approach to the problem of accounting for the current at the cathode of a mercury arc are based on considerations of space charge and of thermal equilibrium. In this paper we wish to point out the significance of some recent work by Guntherschultze on evaporation and conduction heat losses from a cathode and by ourselves on heats of condensation of electrons and positive ions. These latter are important factors in the "energy balance" at the cathode, since the cathode is cooled by the emission of electrons from it and heated by the neutralization of positive ions at its surface. In order to measure these heats of condensation, we immersed a metal sphere in the intensely ionized atmosphere of an arc (in A, N2 or H2 gas) by means of three fine wires, two of which formed a thermojunction to measure the temperature of the sphere, while the third carried the current of electrons or ions flowing to it. We were thus enabled to measure the heating effect produced when either an electron or a positive ion gave up its electric charge to the sphere. For electrons the results were in good agreement with those of other observers by other methods. For positive ions our results are the first experimental determinations which have been made. They indicate that neutralization of positive electricity at the surface of a metal is accompanied by radiation of energy. Finally we used these values to interpret the phenomena at the cathode of a mercury are. By equating all sources of energy input to all sources of energy output, two conclusions of great importance in the theory of the mercury arc are drawn: (1) electrons are pulled out of the cathode by the strong electric forces due to the cloud of positive ions near its surface; (2) mercury lost by the cathode is not all evaporated, but much of it escapes in a spray, as if mechanically extracted.

Magnetic hydrogen atoms and non-magnetic hydrogen molecules: WILLIAM ALBERT NOYES, University of Illinois. Ten years ago the author suggested that two

atoms may be held together by an electron rotating about two positive nuclei. Similar suggestions were made, quite independently of each other, by Sidgwick and Knorr, in 1923. Paulus and Grimm and Somerfeld have, more recently, favored this hypothesis, and Glockler has given it some experimental support by a study of the ionization potential of methane. Quite recently, Phipps and Taylor, by a very ingenious modification of the methods of Gerlach and of Kunz, Taylor and Rodebush, have demonstrated that isolated hydrogen atoms are magnetic while hydrogen molecules are not. These facts may be explained very simply by supposing that in the hydrogen molecule the two electrons rotate in opposite directions in parallel planes with the two nuclei located between these planes. An extension of these principles might possibly explain the formation of helium from hydrogen. It is fully appreciated that the suggestion is very hypothetical and can become of permanent value only in case some one finds a method of subjecting it to a rigorous mathematical analysis and it should be found to be in accord with all the experimental facts by which it may be tested. The successes which have attended the development of Dalton's picture of the atom and the pictures of the structure of molecules proposed by Couper and Kekulé, give us some reason to hope that other pictures may be of service.

Relation of the octet of electrons to ionization: WILLIAM ALBERT NOYES, University of Illinois. In accordance with the theory of electronic structures proposed by G. N. Lewis, simple ions consist of an atom with the exterior octet shell characteristic of the atoms of the noble gases but differing from those atoms because the positive charge of the nucleus is greater or less than the number of electrons in the shell by one or more units. Complex ions have a central atom with a similar structure. As atoms of the noble gases are unable to combine with other atoms because they can not share electrons with them, it is suggested that the similar electronic structure of ions and the repulsion between the outer electrons of the shells of two ions when they approach each other may be one reason why the ions remain apart in solutions and why they have some of the properties of independent molecules.

Exhibit of research results in the Grand Canyon: JOHN C. MERRIAM.

Footprints of unknown vertebrate animals in the Carboniferous and Permian of the Grand Canyon, Arizona: CHARLES W. GILMORE, U. S. National Museum. This paper describes the results obtained from two trips to the Grand Canyon of the Colorado, undertaken for the dual purpose of securing collections of fossil tracks for the U. S. National Museum, and at the same time, to prepare an exhibit of the tracks in situ for the National Park Service. Both of these projects were successfully carried out, a collection of slabs of footprints some 4,400 pounds in weight were secured for the National collections and a track covered area several hundred

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