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Fong Discovered the : Molecular Model of

This post records the author Francis K. Fong's finding of the Calvin cycle, or dark reactions in photosynthesis, as a federal tax conspiracy. It is the subject of an investigation reported on NSFfunding.com's Website enabled by the corroboration of Steve C. Beering, former Purdue president and former chairman of the National Board.

Fig.A. Beering [pictured, center] corroborated [right] that the Calvin cycle is a financially motivated fraud, enabled by Purdue's news release published in Chem. & Eng. News 33, 2809 (July 4, 1955) [left]

On May 15, 1995, Beering wrote, Fig.A:

"In 1951. Purdue Trustees through Roger Branigin acquired the Lawler tract with federal reimbursement funds paid to Purdue Research Foundation, ("PRF") and improved it with additional federal funding obtained upon Purdue's news release of July 1959 (sic 1955), contrary to fact, that the federally funded Lawrence Radiation Laboratory had demonstrated, in vitro, the dark photosynthetic cycle. [See, Fig.A left] Meanwhile, the Trustees built Purdue's Calumet Extension Center on Woodmar Realty land purchased in bankruptcy proceedings presided over by 7th Circuit Judge Swygert, and incorporated Purdue-Calumet Development Foundation ("PCDF")."

Fig.B. Comparision in support of Beering's corroboration that the news story, left, for establishing the dark cycle, reaction (D), left, is contrary to Calvin's original papers on the Berkeley group's experimental proof of reaction (L), right.

For a detailed report on Beering's corroboration of the financial impetus for establishing the Calvin cycle, see, the December 13, 2011 post on the origins of the Calvin cycle.

A proof, that the Calvin cycle resulted from the news release issued by Purdue contrary to the original papers published by Calvin, is shown in Fig.B, in which the news report on Calvin's in vitro demonstration of reaction (D), Chem. & Eng. News (July 4, 1955), is compared with Calvin's original papers on the Berkeley group's finding of the reaction (L), Wilson, A.T. and Calvin, M. (1955) J. Am. Chem. Soc. 77, 5948-5957, providing experimental proof of Calvin, M. and Massini, P. (1952) Experientia 8, 445-484, in which Calvin first proposed that photosynthetic fixation is a light reaction.

Calvin cycle, dark reactions in sunlight

The title of this post, "Francis K. Fong Discovered the Calvin cycle," is not a mistake. Fong, not , discovered the Calvin cycle, or the dark photosynthetic reactions.

The Calvin cycle was the result of a work of fiction on which Calvin based his representation of "the photosynthetic " in his Nobel Lecture at Fig.18, the reaction (D). Although Fig.18 was rejected by Calvin in the same Nobel Lecture, at Fig.20, in favor of the Berkeley group's finding of the reductive reaction, reaction (L), it was reaction (D) that became adopted by the community as tried and true. This reaction (D) became known as the Calvin cycle, as reproduced in Fig.1 below.

Fig.1. Calvin's representation in his Nobel Lecture of the "photosynthetic carbon cycle" based on a work of fiction.

Fong discovers the Calvin cycle

More than half a century ago, during 1958-59, Fong uncovered the photosynthetic dark reactions. He discovered that Mother did plant photosynthesis in the light in the dark. He developed a consuming interest in unraveling this curious phenomenon.

At that time, he studied under Sir Hugh Taylor as an undergraduate major at .

Fig.2. Francis K. Fong aged 20, left, in search of an undergraduate thesis topic in 1958-59, discovered the Calvin cycle attributed to Nobel Laureate Melvin Calvin.

For his undergraduate thesis, Fong pored over the chemical literature for a topic. He was captured by the possibilities of the Centenary Lecture delivered on October 28, 1955 by Melvin Calvin before the Chemical Society (London). (See banner image atop the Calvin Cycle Website.) The lecture was entitled "The Photosynthetic Carbon Cycle," nature's secret for taking up (fixing) and, then, reducing it to organic matter with , energized by stored energy from the sun - all of this in the dark without the help of sunlight.

Photosynthesis, the combination of H2O and CO2 to yield sugar and molecular , is arguably the most important reaction in the study of chemistry. It provides the sustenance of all life on earth; but it had remained an unsolved mystery up to and until 1955, when Calvin by his lecture promised to the world that mankind penetrated this mystery.

In 1958, when he first read, and then pursued, Calvin's remarkable accomplishment, Fong was 20, a junior. He was unprepared for the shocking finding, as he delved into Calvin's unraveling of nature's great mystery. What Calvin called the photosynthetic cycle had apparently originated from a single news story in 1955, that Lawrence Radiation Laboratory (LRL) [Lawrence Berkeley Laboratory (LBL)] workers "performed,"(a) "by a separate collection of soluble chemicals,"(b) all of the reaction steps in the dark photosynthetic carbon reduction cycle:

(a) Chem. & Eng. News. 33, 2809 (July 4, 1955). (b) Calvin, M. (1956) J. Chem. Soc., 1956, 1895-1915.

Article (b) was Calvin’s speech before the Chemical Society based on the newspaper article (a), which was released by Purdue after Wilson and Calvin (1955) reported Berkeley workers' findings to the contrary. Fong continued searching for proof of Calvin's claims, but no such proof existed. But for the news item published in the July 1955 issue of Chem. & Eng. News, all Calvin's own original papers would seem to contradict his proclamations. Carbon reduction in photosynthesis was neither dark nor cyclic!

Unschooled in how scientific research was processed through the media to reach the public, Fong attributed his curious finding to his lack of knowledge as to how important research was reported. There exists a strange fascination in us to wantnature to operate in an unfathomable, mysterious way. Mother Nature does photosynthesis in sunlight in the dark! Or is it possible that Mother Nature has nothing to do with it? In the 1940's, C.B. van Niel of and Berkeley's and had pioneered the concept of reduction in green plants as a dark reaction, in a process akin to bacterial (non- chlorophyllous) systems. Dark chlorophyll photosynthesis was born, summarily dismissing the century-old photochemical theory of carbon reduction in photosynthesis by .

Fong was unable to rationalize why Calvin would publish his finding of the photoreductive path of carbon in plant photosynthesis in reputable journals and, then, rely on a newspaper story to claim his dark cyclic reaction. As a result, Fong chose another subject, also one of topical interest in the late 1950's, for his senior thesis. He entitled his thesis, "The ABC of Nuclear Fusion."

In the spring of 1959, Fong won the Sayre Fellowship for a graduating senior to enter Princeton's graduate program in chemistry. He joined Paul von Schleyer's group to do research in physical organic chemistry. Photosynthesis involves complex organic reactions; to understand why photosynthetic carbon reduction was a dark cyclic reaction, he would first need to master the principles of physical organic chemistry.

Two things happened during Fong's second year in graduate school that would prove eventful in shaping his education as a physical . Early in 1961, on a snowy day, he climbed a window into Clio Hall, Princeton's music department, to do a "rehearsal practice" of Beethoven's C-Minor Third Piano Concerto. Challenged by the forte solo part following the third orchestral tutti passage of the Alegro con brio First Movement, he forgot an aldo condensation experiment he left unattended in Schleyer's lab. When he returned, Schleyer was waiting. Above him were Fong's exploded condensation products splattered onto the the 20-foot high ceiling of Frick Hall. A music lover himself, Schleyer the thesis advisor said something direct but true, sufficiently stern in the delivery that Fong got the message to change his Ph.D. thesis advisor to study under Charles P. Smyth. He completed his dissertation on the dielectric relaxation of polar in organic solvents. Schleyer and Fong remain on the best of terms through the years, but the switch was instrumental in Fong's later work on photosynthesis research using the quantum statistical mechanical approach to molecular relaxation. Not long after the exploded experiment, also in 1961, Calvin won the in Chemistry for the dark reaction cycle in photosynthesis.

There was euphoria in the air. By Calvin's Nobel Prize, there would be factories the world over for manufacturing all kinds of organic compounds from the free, inexhaustible sources: sunlight, water from the oceans and carbon dioxide in the air. Calvin by his lecture did change the world in a most profound manner, including this author's - but not in the way he promised by his lecture in October of 1955.

Calvin and Fong - lives in parallel

The development of the Calvin cycle bore an eerie parallel to Fong's school days and professional life long before 1961, when Calvin received the Nobel Prize and Fong exploded his aldo condensation.

Before Fong knew the meaning of the word, "chemistry," through the 1940's, Calvin, James Bassham and proposed that photosynthesis was a dark reaction cycle. See, e.g., Wikipedia's one and only reference to the original literature for its Calvin cycle page:

Bassham J, Benson A, Calvin M (1950). "The path of carbon in photosynthesis." J Biol Chem 185 (2): 781– 7. PMID 14774424.

The Calvin cycle originates from Calvin's unrefereed lecture delivered on October 20, 1955, a few months after Fong graduated with the Class of 1955 from St. Louis Boys School in Hong Kong. A year later, in 1956, when Fong matriculated from Wah Yan College, Hong Kong, this unrefereed lecture appeared in print, Calvin, M. (1956) J. Chem. Soc. 1956, 1895, the progeny of a work of fiction by a Purdue instructor by the name of Dale Margerum depicting the Berkeley group's experiments contrary to Calvin's original papers on reductive .

Fig.3. Benson's letter of May 1981 to Fong: Fong's uncovering of the Calvin cycle: From left, Calvin, Benson (1954), Fong (1959) and Bassham.

The Calvin cycle unraveled through the decades, Fig.3. In 1955, Wilson, A.T. and Calvin, M. (1955) J. Am. Chem. Soc. 77, 5948-5957, Calvin showedexperimental proof of the designation, in Calvin, M. and Massini, P. (1952),Experientia 8, 445-484, of the carboxylation reaction as a light reaction.

In 1958-59, Fong found that Calvin, M. (1956) J. Chem. Soc. 1956, 1895, was based on the Chem. & Eng. News story, contrary to Wilson and Calvin (1955) and Calvin and Massini (1952). That year, in Calvin & Pon (1959), J. Cell. Comp. Physiol., 54, Suppl. 1, at 65-67, Calvin concluded that RuBisCO, ribulose-1,5- bisphosphate carboxylase-oxygenase, is possibly not the for the observed reductive splitting, reaction (L); that, in fact, "the reductive splitting of the intermediate carboxylation product might very well require a reducing system as yet unknown."

A year later, Bassham, J.A. and Kirk, M. (1960) Biochim. Biophys. Acta, 43, 447- 464confirmed Calvin and Pon (1959).

Meanwhile, Benson continued to espouse the dark reaction cycle, Fig.3. It turned out that Benson was dismissed by Calvin in December 1954. Presumably, Calvin thereafter kept Benson in the dark as to the Berkley group's experimental findings dating from Wilson and Calvin (1955).

Fong's model for photosynthesis

Fig.4. DOE arranged for Fong and Calvin to discuss the Calvin cycle in view of Fong's demonstration of red-light Photosynthesis of organic fuels from H2O and CO2.

During the early 1970's, Fong toured the Far East, visiting and giving lectures at Tsing Wah University, Taiwan, and the Chinese University, Hong Kong, on his statistical quantum mechanical theories of molecular relaxation and rare-earth upconversion experiments. There he crossed paths with Calvin, who gave highly publicized lectures on his energy scheme for planting sugarcane for conversion to ethanol as an alternative energy.

Fig.5. Fong, Francis K. (1974) PNAS, 71, 3692-3695.

Fig.6. The C2-symmetric Chl a reaction center.

Upon return to West Lafayette, Fong published his first paper on photosynthesis. Fong, Francis K. (1974)"Molecular Basis for the Photosynthetic Primary Process," Proc. Nat. Acad. Sci. USA, 71, 3692-3695, Fig.5.

In Fong (1974), he predicted that the chlorophyll a reaction in photosynthesis is a C2-symmetric adduct structurally similar to the hydrated Chl a dimer, in which the two Chl a molecules are cross-linked by Chl a carbonyl-water bonds, with the water coordinated to the Chl a Mg , Fig.6.

In this paper, Fong proposed an exciton model for a two-photon interaction, Fig.7. A singlet-triplet annihilation, enhanced by symmetry selection rules in a C2-symmetric chlorophyll a dimeric adduct, enables the red-light upconversion photoexcitation of the reaction center Chl a dimer. Thereby, the photosynthetic primary process is activated for the reduction of CO2 by the water to make organic fuels.

Significantly, the reaction center structure of bacterial photosynthesis and that of the PS II reaction center, that which is responsible for the water splitting reaction in plant photosynthesis, have since been found to be C2- symmetric dimeric adducts.

Discussions at Asilomar - molecular model and sugarcanes

Fig.7. Photon upconversion in C2 Chl a adduct.

Based on his theoretical model, during the second half of the 1970's, Fong and his co-workers demonstrated in vitro the red-light photosynthetic chlorophyll water splitting and carbon reduction reactions.

This demonstration, in 1978, was important, because at that time it was generally believed that red light did not support sufficient "emf at pH 7" to reduce carbon dioxide with the hydrogen from water to make polyatomic organic matter.

In 1978, Energy Department Deputy Energy Research Director Doug Pewitt sent Fong, as a DOE observer, to attend the DOE-sponsored conference featuring Calvin's energy scheme for growing sugarcane plants in Brazil for solar conversion as an alternative energy. The conference took place at Asilomar, .

There Fong visited with Calvin, then head of LRL Chemical Biodynamics, whoconcluded in Calvin, M. (1964) "The path of carbon in photosynthesis." The Nobel Lecture, delivered on December 11, 1961, From Nobel Lectures, Chemistry 1942–1962. Elsevier Publishing Company, Amsterdam, pp 618–644 at 638:

"Here [in reaction (D)] the intermediate is split by hydrolysis to two molecules of phosphoglyceric acid. However, in our earlier work the possibility of a reductive fission [in reaction (L)] at the same point to give one of triose and one molecule of phosphoglyceric acid was considered. It was rejected in favor of the hydrolytic splitting because of our failure to find any evidence of the intermediate. However, more recent, very careful kinetic analysis of the carbon flow rates by Dr. James A. Bassham has suggested that the reductive split may indeed participate in the reaction to some extent while the light is actually on." (emphasis in bold added)

At Asilomar, Fong directed his discussion with Calvin to a question of the DOE-sponsored conference on Calvin's scheme for planting sugarcanes in Brazil, rather than the dark photosynthesis of organic fuels from water and carbon dioxide. After all, didn't Calvin in Calvin, M. (1956) promise the world of such photosynthesis? Given that Calvin and Fong were in agreement that photosynthetic carbon reduction, in vivo or in vitro, was neither dark nor cyclic, the discussion on sugarcanes was not particularly productive; and Fong and Calvin turned to tracing the Calvin cycle to its extraordinary origins: Purdue trustees'development with MIT of the Blue-Book formula, which availed federal reimbursements from federal funding of the Calvin cycle and Purdue-Calumet Development Foundation's East Chicago Federal Loan and Grant Contract for financing the Munster Plains development. Warned Calvin, "I had no choice in the matter. You have a large following now. But unless you go along, 'they' can, and will, terminate your research."

Calvin and Fong - the final agreement

In Calvin, M. (1964) at 639, Fig.20, Calvin ruled out the hydrolytic splitting in favor of an asymmetric reductive fission of the intermediate to yield one molecule of PGA, phosphoglyceric acid, and one molecule of the triose PGL, glyceraldehyde . Calvin's reductive path of carbon is reproduced below, Fig.8(A).

In 1988, Fong in Fong, Francis K. and Butcher, Karen A. (1988) Biochem. Biophys. Res. Commun., 150, 399-404, showed the non-equivalence of the "upper" and "lower" 3-C fragments in the 6-C intermediate. In 1989, Fong et al published amolecular mechansim for the reductive path of carbon in photosynthesis reproduced above in Fig.8 (B). F.K. Fong, K.A. Butcher, A. Agostiano, M. Della Monica, M.S. Showell, and J. V. Schloss (1989), "Coupling Between the Light and Dark Reactions of Oxygen and CO2 Fixation in Photosynthesis: Early Experiments in Photosynthesis Revisited," in Enzymatic and Model Carboxylation and Reduction Reactions for Carbon Dioxide Utilization, Eds. M. Aresta and J.V. Schloss, Series C: Mathematical and Physical - Vol. 314, NATO ASI Series Advanced Science Institutes Series, Kluwer Academic Publishers, Dordrecht/Boston/London.

In Fig.8(B), carbon fixation in photosynthesis is regulated in two kinetically coupled pathways. They involve a pair of non-equivalent, enzyme-bound PGA molecules obtained from RuBP carboxylation. The first is a non- cyclic pathway for the direct of from the ["lower"] 3-PGA obtained from the C-3, C-4 and C-5 fragment of the six-carbon carboxylation adduct. The second involves the Mg2+-bound ["upper"] 3-PGA molecule formed from the C-1, C-2 and C-2' fragment of the 6-C intermediate, which is released and subsequently reduced, with the intervention of the NADPH and ATP - in a Calvin-cycle-like metabolic path - to regenerate the RuBP. Thus, Fong and Calvin came into complete agreement as to the asymmetric split of the 6-C intermediate into one molecule of PGA and one molecule of triose, as shown in Fig.8, which displays side- by-side the final conclusions of (A) Calvin (1964) and (B) Fong et al (1989).

Fig.8. (A) Calvin (1961); (B) Fong et al (1989).

For the National Science Foundation's finding of 1989 for Fong's discovery of the Calvin cycle, backed by the disclosures of National Science Board members Steven C. Beering and France A. Cordova, of how the Calvin cycle was established contrary to Calvin's finding of the light carboxylation reaction, please go to NSFfunding.com's Synopsis site, the Calvin Cycle Website.

By this finding of the NSF, as of 1989, all questions as to the Calvin cycle being an extraordinary NSF fraud case were, or should have been, settled. As it turned out, Fong was wanting in a yet another branch of learning, that of the economic model for public corruption pioneered by Richard A. Posner.

Fong has since penetrated this final branch of learning. It remains to be seen whether time has at long last arrived for a reckoning of the strange life span of the Calvin cycle, a modern wonder of doing photosynthesis in the dark, an improbable achievement, a Ponzi scheme of unparalleled dimensions - against all odds and common experience - and all experimental observations and theoretical calculations.