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The Path of Carbon in Photosynthesis (XX EXPERIENTIA Vol. VIII - Fase. 12 Pag. 445-484 15. XII. 1952 The Path of Carbon in Photosynthesis (XX. The Steady State) By M. CALVIN and P. MASSlNI2, Berkeley, Cal. Photosynthesis, the process by which green plants separation may be represented in the following chart are able to capture electromagnetic energyfin the form (Fig. 1). The essential feature of the separation is the of sunlight and transform it into stored chemical energy independence of the photochemical part of photosyn- in the form of a wide variety of reduced (relative to thesis from the carbon dioxide reduction part. We shall carbon dioxide) carbon compounds provides the only not here even try to outline all of the various forms of major source of energy for the maintenance and pro- evidence Which have been adduced in support of such pagation of all life. For this and other reasons, the a scheme but only to point out additional bits which study of the nature of this process has been a very have been added in recent years and particularly those attractive area for many years and a wide variety of which stem from our own work'. scientific interest and backgrounds have been brought to bear upon it. These range from the purely biological (CH20) 0 to the strictly physical with the biochemical and phy- sicochemical area lying between. Important contri- butions to the understanding of the phenomenon have come from all these areas, but in spite of the enormous amount of work and study that has gone into the prob- lem, relatively little is known, or rather understood, about the fundamental character of the process even C02 • 2 0 ," "9 today. It is perhaps pardonable that one engaged in L ." _j studies in this area tends'to the conclusion that most of Fig. 1. the knowledge has been acquired in the relatively recent past. Discounting that tendency, it still seems fair to Tile scheme itself is an outgrowth of proposals of say that we have only just begun in the last decade or some fifteen years ago by VAN NIEL 2 resulting from his so to gain some understanding of the intimate details studies of the comparative biochemistry of photosyn- by which the basic process represented in the overall thesis. More recently, the photochemical apparatus has reaction been shown to be separable from the rest of the plant +hv by the experiments of Hill 3. C02 + H20 ~ 02 + (CH20)~ He was able to make prepardtions of chloroplasts < -- Energy and chloroplastic fragments which, upon illumination in the presence of suitable oxidizing agents other than has come to be understood. The recognition of this carbon dioxide, were able to evolve molecular oxygen. overall reaction as written, to represent the basic nature Still more recently, OCHOA an others 4 were able to of-the process of photosynthesis, and, further, that its demonstrate that these same preparations were capable reversal represents the basic reaction of respiration is, of using coenzyme I and II (D.P.N. and T.P.N.) as of course, an old one. As a result of more recent study, it has been possible x M. CALVIN and A. A. BENSON, Science 107, 476 (1948). - A. A. to separate the process of photosynthesis into two dis- BENSON and M. CALVtN, Cold Spring Harbor Symp. quant. Biol. 13, tinct and separate parts. The gener.al features of this 6 (1948). - M. CAt.VlN and A. A. BENSON, Science 10.9, 140 (1949). 2 C, B, VAN NIEL, Photosynthesis in Plants, Chapter 22 (Iowa State College Press, Ames, Iowa, 19.19), pp. -t37--195. 1 The work described in this paper was sponsored by the U.S. a R. HILL, Nature 139, 881 (19.17); Prec. roy. See. (London) [B] Atomic Energy Commission. 127, 192 (1939).- R. HZLL and R. SeARISBRICK, Nature 146, 61 (19,t0). 2 Radiation Laboratory and Department of Chemistry, Univer- 4 W. VISHtCIAC and S. Octm*, J. Biol. Chem. 196, 75 (1952). - sity of California, Berkeley. Fellow of the Swiss Foundation, D. I. ARrCON, Nature 167, 1008 (1951). - I.. J. TOLMAClt, Arch. Bio- ,,Stiftung ffir Stipendien auf dem Gebiete tier Chemie~,, 1951-1952. chem. Biophys. 83, 120 (1951). 446 M. CALVIn and P. MASSINI: The Path of Carbon in Photosynthesis [ExPERIENTIAVOI..VIII/12] suitable oxidizing agents leading to the evolution of duced by the presence of carbon dioxide in those cases oxygen. Furthermore, the experiments of RUBE~ 1 in whic.h the carbon dioxide fixing system is still pre- showed that the molecule of oxygen evolved in photo- sent. However, when the carbon dioxide system has synthesis had its proximate origin in the oxygen of been removed, as is true in the case of chloroplasts, the the water molecule and that the oxygen atom associ- luminiscence becomes independent of carbon dioxide. ated with the carbon dioxide must first pass through While it thus appears that the unique problem of water before arriving at gaseous oxygen. From the chart photosynthesis lies in the right hand half of the chart it may be seen that the ultimate result, then, of the of Figure 1, the present discussion will be limited to photochemical reaction initiated by the absorption of the other side of the chart, that is, the path through light by the chlorophyll molecule is the division of the which carbon passes on its way from carbon dioxide to water molecule into an oxidized part which ultimately all the raw materials of the plant. It is essentially a leads to molecular oxygen and some reduced parts study of what we now believe to be entirely dark represented in the chart by [Ht. reactions and might best be characterized as phyto- This reduced part [H l we have called "reducing synthesis. This area not only has a great interest for its power" because as yet it is not possible to state specifi- own sake but would almost certainly cast some light cally what form or forms it may be in. This reducing upon the nature of the reducing agents which arrive power is capable of reducing carbon dioxide in the from the photochemical part of the reaction and drive absence of light; that is to say, that the reduction of the carbon cycle toward reduction. The reason for this carbon dioxide itself is a dark reaction. This was indi- particular interest lies in the fact that we have, in recent cated first in the earlier experiment of McALISTER ~ in years, come into possession of a tool which is especially which he was able to show that following a period of suited for this study, namely, labeled carbon atoms in photosynthesis a number of plants continued to absorb the form of a radioactive isotope of carbon, C 14. All of carbon dioxide for a short period (seconds to minutes) the results that will be described later were made after cessation of illumination. We were able to demon- possible through the use of this labeled carbon dioxide. strate this in an even more direct and unequivocal With such a labeled molecule available, the design of fashion and generalize it for all plants so far tried when an experiment for determining the sequence of com- we were able to show that not only did all of these pounds into which the carbon atoms of carbon dioxide plants absorb quantities of carbon dioxide in the dark may pass during the course of their incorporation in the after illumination but that the products formed in the plant is, in its first phase, a straightforward one. dark were qualitatively and under certain conditions quantitatively similar to those formed in a fairly com- h~ % parable light period s . The method used for this demon- T stration was the same as those to be described later in l LEAF the review. The lifetime in the dark of this reducing power which is generated by light is also of the order of seconds to minutes and almost certainly corresponds C02 , to a concentration of one or more definite chemical species. It is quite conceivable, as mentioned earlier, 1 that some of it might be in the form of reduced coen- ~o2 T zymes. H~ (CH20) Very recently it has been reported 4 that both the Fig. 2. higher plants and isolated chloroplasts emit a chemi- luminiscence following cessation of illumination. This We may visualize the problem in terms of the chart chemiluminiscence has a decay time which corresponds in Figure 2 in which the green leaf is represented very closely to that which we have observed for the schematically as a closed opaque container into which reducing power. In fact, it would seem almost surely stream the raw materials of photosynthesis, namely, to represent the reversal of the conversion of electro- carbon dioxide, light and water containiiag the neces- magnetic into chemical energy, namely, the transfor- sary mineral elements. From this container are evolved mation of at least some of the chemical energy stored tile products of photosynthesis--oxygen gas and the in the reducing power into the electromagnetic energy reduced carbon compounds constituting the plant and of luminiscence. Furthermore, the luminiscence is re- its stored reserves. Heretofore, it has been possible to study in a quantitative way the nature of the process 1 S. RUBEN, M. RANDALL, M. D. KAMEN, and J. HYDE, J. Am. going on inside the opaque container only by varying Chem. Soc. 63, 877 (1941). 2 E. D. MCALtsTER and J. MYERS, J. Smithsonian Inst. Pubt. external conditions and noting variations in the final (Misc. Coil.) 6, 99 (1940). products. Although there has been no serious doubt 3 M. CALVIN, J.
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