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Cordova's Finding: Affirming NSF's Definition of Francis K. Fong's Discovery of Margerum's Work of Fiction that Begot the Calvin Cycle and its Z scheme

A. Calvin Cycle Discussion on -Online.Org's Forum

This post complements NSFfunding.com's Website on Calvin cycle, the dark reactions in .

There is an interesting discussion on biology-online.org/biology-forum under the title, "the Calvin cycle???help please." First, the universally accepted interpretation of the Calvin cycle is described: "NADPH is actually electron provided and made blablabla, not . And last, but not least this triose called glyceraldehyde is primarily recycled, that's why is it called 'The Calvin CYCLE,' and why it can work all the time - Just a minor part is transformed to hexose (primarily fructose), the rest has nothing to do with the Calvin cycle."

Then, Biology-Online.Org's discussion departs from the accepted interpretation, in that , to whom is attributed the Calvin cycle, or the dark reactions in photosynthesis, had nothing to do with the Calvin cycle. The reason is because Calvin and his group at Berkeley published, in their original papers, findings from their C-14 tracer experiments that the "triose called glyceraldehyde phosphate is NOT recycled." Calvin et al reported a reaction in photosynthesis which is neither dark nor cyclic, but a photoreductive reaction. The CO2 assimilated from the air by the RuBP (ribulose bisphosphate) results in reductive splitting of the 6-C intermediate into one of PGA (phosphoglycerate) and the other a triose, glyceraldehyde phosphate, which condenses to make and, then, .

This post provides a detailed analysis of the author Francis K. Fong's discovery of the Calvin cycle, or, the mechanism by which the Calvin cycle, or the dark reactions in photosynthesis, came into being.

B. The Calvin Cycle, an Unlikely Fraud

This post and the above quote on the Calvin cycle as an imperishable fraud should be read in conjunction with the National Science Foundation OIG's determination upon NSF's explanation of Fong's discovery of the Calvin cycle, the dark reactions in photosynthesis - a work of fiction by a Purdue instructor.

The NSF explains the discovery in terms of negligence for its flawed review of Fong's NSF proposal, No. DCB 8822928. The explanation was followed by NSF OIG's determination, that the Calvin cycle was a fraud. Unfortunately, this determination was complicated by countermeasures to State Director Keith Luse's (Lugar) commitment of a GAO review, which resulted in the killing of Don MacLauchlan, vice-president of Reduction, sponsor for DCB 8822928.

This post follows closely NSF Division Director Bruce Umminger's reading of the original papers by Calvin et al; and was necessitated by the belated corroboration, an independent finding by Purdue President and NSB (National Science Board) member France A. Cordova, done in response to Fong's request to clarify PEFCU's payment, in 1978, of the $48,903.81 from Treasury to revenue officers and NSF OIG employees.

The Calvin cycle as an unlikely false claim by a Purdue instructor differs qualitatively from a second, equally improbable false claim by another Purdue researcher, something called the "tabletop thermal bubbles for nuclear fusion involving high-energy particles." Whereas the "tabletop thermal bibles" as a fraud, like most frauds in science, was exposed by the work of others in the field, the Calvin cycle was embraced by those who knew it as a fraud by their own finding of the light carboxylation reaction. Former Purdue President and NSB chairman Steve Beering on the PX 45 tape attributed this difference to the Calvin cycle as the product of a secret procedure called the Blue-Book formula, a money-making proposition by which Purdue trustees used federal reimbursement moneys from PCDF's (Purdue-Calumet Development Foundation) East Chicago Loan and Grant Contract to invest in the Munster Plains real estate development, as described in Fong's reports of 1995 and 1996 to IR Commissioner Richardson.

In the discussion to follow, Fong reproduces NSF's determination of 1989, of how a work of fiction became the Calvin cycle, the universally acclaimed "synthesis in the light of biomass from and in the dark." He reports the NSF's demonstration of how the Calvin cycle became established, not by reviewer negligence on the part of NSF program directors, but by a knowing, patterned activity calculated to penetrate the United States Treasury.

C. Margerum's Work of Fiction that Became the Calvin Cycle

I. Differentiating Carboxylation Reaction in the Dark (D) from that in Light (L)

In the Calvin cycle the uptake of carbon dioxide by the 5-carbon ribulose bisphosphate, RuBP, results in the release of two of the 3-carbon D-glycerate-3-phosphate, 3-PGA.

With the "high-energy phosphoanhydride bonds" in the ATP, , and the reducing agent, NADPH (the reduced form of NADP+, nicotinamide adenine dinucleotide phosphate) obtained from the "Z- scheme of light reactions," the 3-PGA molecules from the RuBP carboxylation then undergo thermally activated reduction in the dark to sugar. Meanwhile, the C-14 experiments by the Berkeley researchers led them to the conclusion that the RuBP carboxylation reaction in the light results in the photoreduction of carbon without the participation of ATP. A review of this finding, which is briefly summarized below, was published in the definitive research monograph on this subject, Bassham,J.A. and Calvin,M. (1957) "The Path of Carbon in Photosynthesis," Prentice-Hall, Inc., Englewood Cliffs, N.J.

In 1952, Calvin reported [Calvin,M. and Massini,P. (1952) Experientia 8, 445-484] the formation of PGA in an overall reaction requiring RuBP and carbon dioxide. He delineated two pathways for the uptake of one carbon dioxide molecule by the 5-carbon RuBP. In the light, the carboxylation reaction resulted in the formation of one mlecule of PGA and one of triose, a three-carbon molecule at the sugar oxidation level, but that in the dark gave two molecules of PGA.

Fig.1. Wilson and Calvin (1955)

In June of 1955, Calvin submitted a manuscript for publication in the Journal of American Society [Wilson,A.T. and Calvin,M. (1955) J. Am. Chem. Soc. 77, 5948-5957], Fig.1, in which he reported detailed experimental procedures in corroboration of Calvin and Massini (1952).

Wilson and Calvin (1955) showed proof (pictured right) of the designations in Calvin and Massini (1952) of the two different fates of the carboxylation reaction in the light (L) and dark (D). The two reaction pathways are schematically shown below:

RuBP + CO2 ────> Triose →→→ (L) | ──> 3-PGA

RuBP + CO2 ────> 3-PGA + 3-PGA (D)

+ CO2 ────> 2 3-PGA (D) II. Grutzner's Exposition of the Photosynthetic Path of Carbon

Fig.2. Purdue's affidavit.

At this point, Fong presents John Grutzner's elegant explanation, Fig.2, in a few words, of the seemingly convoluted development (1952 to the present) called the Calvin cycle.

Reaction (D) was established by Horecker et al (1956) [Weissbach.A., Horecker,B.L. and Hurwitz, J. (1956) J. Biol. Chem. 218, 795-810] and Ochoa et al (1956) [Jakoby,W.B., Brummond,D.O., and Ochoa, S.J. (1956) J. Biol. Chem. 218, 811-822], who reported its occurrence in the dark, using purified (RuBP carbolase/oxygenase) preparations outside of the living plant.

The in vitro demonstration of reaction (D) was important, because its characterization provides a comparison and contrast for the Wilson and Calvin's observation of in vivo carbon reduction as the light reaction (L). In in vivo experiments using living plant cells, Wilson and Calvin could find no evidence of reaction (D). Instead, they found only reaction (L), in which only one half of the product appears as the PGA, whereas the other half is directly reduced in the light to yield triose, and then sucrose. Wilson and Calvin described reactions (L) and (D) as endergonic and exergonic, respectively; the reduction of the PGA from (D) would require ATP and NADPH, whereas (L) would occur spontaneously in the light. These authors further observed that photosynthetic carbon reduction to produce sucrose occurs in a non-cyclic reaction, while the PGA produced in reaction (L) enters into the dark reactions of the reductive pentose phosphate cycle to regenerate the 5-carbon RuBP. Reaction (L) thus provides a direct coupling between the light and dark reactions in plant photosynthesis. Calvin et al's observations of the properties of reaction (L) in Wilson and Calvin (1955) and in their extensive subsequent studies were summarized by Calvin, see, Calvin,M. and Pon,N.G. (1959) J. Cellular Comp. Physiol., 54, Suppl. 1, 51-74. The original papers by Calvin et al provided the basis for the Fong- Butcher model (1988) of photoreductive carbon fixation in photosynthesis.

On 9-4-10, Grutzner provided Fong with an elegant, but simple, explanation (pictured above left) of the Fong- Butcher "correction" of Calvin's differentiation, Calvin and Pon (1959) at Fig. 27, of Reaction (L) from Reaction (D).

Summing up, in Calvin and Massini (1952) and Wilson and Calvin (1955), Calvin described Reaction (L) as one occurring in the light, in which the PGA undergoes photoreduction to triose without the intervention of the ATP and NADPH.

III. How Margerum's Work of Fiction Became the Calvin Cycle

Fig.3. 14th ACS NOS program.

Upon J. Am. Chem. Soc.'s receipt on 6-20-55 of the Wilson and Calvin manuscript, on a following Wednesday morning, Calvin presented his findings at the Lawrence Radiation Laboratory of the carboxylation Reactions (L) and (D) in the prestigious 14th ACS (American Chemical Society) National Organic Symposium (NOS) held at the Chemistry Department of Purdue University, Fig.3.

On 7-4-55, the ACS newspaper, Chem. Eng. News 33, 2809 (July 4, 1955), Fig.4, published a story released by Purdue Chemistry instructor Dale W. Margerum. The story established as true and tried the dark reaction cycle in photosynthesis today known as the Calvin cycle.

Fig.4. Margerum's work of fiction.

Purdue's story published on 7-4-55 correctly reported that it was based on Calvin's presentation of Wilson and Calvin's experiments in the 14th NOS held at Purdue, which appeared later that year in print in the Journal of American Chemical Society as Wilson and Calvin (1955). But in Wilson and Calvin (1955) J. Am. Chem. Soc. 77, at 5954, (see image shown above) Calvin discussed "the possibility that both (D) and (L) may be alternative fates for the primary carboxylation product P," (L) being "the direct reductive splitting of P presumably not involving ATP [that] might be expected to be more efficient." Unfortunately, the Chem. Eng. News was based on Purdue instructor Dale Margerum's work of fiction, as follows states facts other than published in Wilson and Calvin (1955) and Calvin and Massini (1952):

"Each of the steps in the photosynthetic carbon dioxide reduction cycle has been determined, and it is now possible to define reagent requirements to maintain it.

"The requirement for reduction of one molecule of carbon dioxide is four equivalents hydrogen and three molecules of adenosine triphosphate (ATP). Photochemical reactions must be the suppliers of these." In Calvin and Pon (1959), Calvin's final experimental report corroborating Reaction (L), was a reference to an abstract published in the 135th Natl. Meet. Am. Chem. Soc., p. 11F. That reference appeared in print as Bassham,J.A. and Kirk,M. (1960) Biochim. Biophys. Acta 43, 447-464, in which Bassham and Kirk observed:

"When Calvin and Massini (1952) reported the formation of PGA in an overall reaction requiring ribulose [bis]phosphate and CO2 they proposed that the reaction in the light gave one molecule of PGA and one of triose phophate [reaction (L)] but in the dark gave two molecules of PGA [reaction (D)]. Wilson [and Cavlin (1955)] discussed this possibility further ***. We shall present here an argument, based on kinetic data, which indicates that the carboxylation of Ru[B]P in vivo during photosynthesis gives rise to only one molecule of 3- PGA."

These authors thus aptly concluded Berkeley researchers' work establishing Calvin and Massini's finding of Reaction (L). This work spanned the entire decade of these researchers' celebrated C-14 tracer studies beginning with Calvin and Massini (1952) and ending with Bassham and Kirk (1960), literally up to the eve of Calvin's receiving his 1961 Nobel Prize for the photosynthetic dark reaction, Purdue's work of fiction that became the Calvin cycle.

Unfortunately, all of that laborious work was wiped out, as the fictitious account published by Margerum in the news media became established as the Calvin cycle, the dark photosynthetic reactions.

D. The Bassham-Benson-Calvin Cycle

In the opening sections of this work, the author observes that the Calvin cycle as a fraud is different than other frauds in scientific research. Here, Fong demonstrates the unlikely phenomenon, in which workers, who know that the Calvin cycle in photosynthesis is a fraud by their own finding of the light carboxylation reaction, embrace it.

In the winter of 2009-10, the editors of the Journal of C Barbara J. Garrison Festschrift invited Fong to contribute to the preface of the special issue, a biosketch of Garrison. See, J. Phys. Chem. C, 2010, 114 (12), pp. 5241–5246.To reconstruct the lost details of the years 1976-79, Garrison's tenure at Purdue, Fong wrote for Cordova's help. The issue turned on a suggested literature survey by Purdue pertaining to PEFCU's transfer, in 1978, of the $48,903.81 in furtherance of the Calvin cycle as the dark reaction cycle in photosynthesis.

On 2-1-10, Fong received from Michael J. Fosmire, Purdue's Head Librarian, an email, (hereinafter "Cordova") Subject: RE: Fw: Access to Library materials - preface for JPC C Barbara Garrison Festschrift. At Cordova's behest, Fosmire wrote to ascertain a conclusion as follows pertinent to the bubbles research and the PX 45:

"I did do a brief search of the terms you mentioned below, in the Web of Science (which indexes the most important research journals from 1900-present). A search of 'dark reaction cycle' AND 'photosynthesis' yielded no results in the database. A search of 'Calvin Cycle' returned several hundred results. The 'Calvin Cycle' appears to be in common usage, for example, an About.com entry: http://chemistry.about.com/od/lecturenotes13/a/photosynthesis_4.htm."

In response, Fong wrote to follow up on the implications: (Cordova at 2)

"Pending your further search assignment to Fosmire, the results he produced should serve our purpose of arriving at an idea of how Dale Mrgerum's release of the Chem. Eng. News story (July 4, 1955) impacted the world community's understanding of photosynthesis."

"I googled 'dark reaction cycle' AND 'photosynthesis.' For your convenience, I attach Results 1- 10 (Cordova at 4-5) of about 59,700 results. Fosmire has thus shown proof that Dale's authorship of the Chem. Eng. News story (July 4, 1955) contrary to Wilson and Calvin (June 25, 1955) may have created a scientific freak of unspeakable dimensions."'

Cordova's finding, that Purdue's claim for the Calvin cycle has nothing to do with this country's research in alternative energy, supports the patterned activityreported by Hunter in his complaint filed with IRS Internal Security and Exempt Organization, consistent with Beering's disclosure for PCDF's promotion of PRF's sale of the Lawler tract.

This patterned activity led Govindjee, among other dark photosynthesists, to use certain alleged "light" with energy in "EMF Units at pH 7" to do a Z scheme of "light reactions." The Calvin cycle, i.e., the dark reaction cycle "in the ," as follows cooperates with the light reactions "in the ," The light reactions provide "ATP and NADPH to the Calvin Cycle, and the cycle returns ADP, Pi, and NADP+ to the light reactions." The reducing equivalents from the ATP and NADPH from the "light reactions" convert, "in the dark," the PGA from the Calvin cycle to the sugar level.

Fig.5. Bassham-Benson-Calvin cycle.

Over the years, Fong corresponded extensively with Govindjee and Don Bryant, another dark photosynthesist, in an attempt to understand the dark and its attending "light reactions." Govindjee specializes in the Z scheme, and is the author and editor of more than "70 research monographs" on the subject. In support of his BDPP (Dark Bacterial Photosynthesis in Plants) scheme, Bryant wrote profusely to document his and Govindjee's rationale for renaming "the Calvin cycle," shown schematically in Fig.5, as "the Bassham-Benson- Calvin cycle."

The point of this review is that the dark reaction cycle as a fraud is not the same as other frauds in science and engineering. Bassham (pictured above) apparently welcomed Govindjee and Bryant's campaign to rename the Calvin cycle to include his name. In striking contrast, Bassham in the above-quoted passage in Bassham and Kirk (1960) clearly made a showing of his knowledge of the Calvin cycle as a fraud. After all, Bassham and Calvin (1957) spearheaded an "important" new direction for photosynthesis research as follows:

"An important question regarding the carboxylation reaction is whether the addition product splits to give two molecules of PGA [as in the Calvin cycle], or whether only one molecule of PGA is formed, the other half of the addition product being reduced directly in the light to triose phosphate."

Therefore, Cordova should complete her further finding to ascertain whether the six decades of the Calvin cycle's dominance resulted in the Z scheme of "light reactions," Fig.6, whether the proliferation of "research books" had resulted from the knowing act on the part of their authors and editors to ignore the entire body of experimental studies by Bassham, Benson, Calvin and their co-workers.

Fig.6. The Z scheme by Govindjee, in which light energy is measured by "emf's at pH7."

E. Conclusion

In conclusion, the United States' losses arising from the Calvin cycle are compounded by the community's reliance on the patterned activity reported by Hunter. From this activity arose the Z scheme of two systems, ("P700") and photosystem II ("P680"), embraced by proponents of the Calvin cycle, including those who know, or should have known, better. The Z scheme connects, oddly, a series of "light reactions," in which the alleged "light" is measured not in electron volts, but "in terms of oxidation-reduction potentials (Em) at pH7."

Fong's demonstration of the in vitro chlorophyll water-splitting and carbon dioxide reduction reactions in red light, shown below, serves a useful purpose in accounting for Calvin et al's carboxylation in vivo in the light (L). Even so, dark photosynthesists persist in arguing that red light in a single chlorophyll photosystem does not have sufficient "emf at pH7" to split water and reduce CO2. The Z scheme of two photosystems continues unabated as the "light reactions in photosynthesis" for "storing light energy" in the form of ATP and NADPH, which "cooperate with the dark reactions" in reducing PGA from the Calvin cycle to "make sugar in the dark."

It is believed that all of this kind of "research" is funded by the National Science Foundation on account of Margerum's work of fiction that became the Calvin cycle.

Appendix: Bennett's Two-Pronged Test Question

In view of Cordova's finding, Fong posed for her proper response the two-pronged question (originally designed in the fall of 1989 by Clifford Bennett, NSF OIG Assistant Inspector General for Audit) as follows:

1. Do the published studies in reputable research journals, Calvin,M. and Massini,P. (1952) Experientia 8, 445- 484Refs. 6-10; Wilson,A.T. and Calvin,M. (1955) J. Am. Chem. Soc. 77, 5948-5957; Bassham, J.A., Shibata, K., Steenberg, K., Bourdon, J. and Calvin, M. (1956) J. Am. Chem. Soc., 78, 4120-4124; Vishniac, W., Horecker, B.L., and Ochoa, S. (1957) Adv. Enzymol. 19, 1-77; Bassham, J.A. and Calvin, M. (1957) "The Path of Carbon in Photosynthesis," Prentice-Hall, Inc., Englewood Cliffs, N.J.; Calvin, M. and Pon, N.G. (1959) J. Cellular Comp. Physiol., 54, Suppl. 1, 51-74; and Bassham, J.A. and Kirk, M. (1960) Biochim. Biophys. Acta, 43, 447-464; represent the entire body of Calvin et al and others' published work on the path of carbon in photosynthesis, on which was based the Fong-Butcher model, Fig.2?

2. Are there other studies than Margerum's story [(a) Chem. Eng. News. 33, 2809 (July 4, 1955), on which was based Calvin's Centenary Lecture before the Chemical Society in London, (b) Calvin, M. (1956) J. Chem. Soc., 1956, 1895-1915] that would support a conclusion of the dark reaction cycle, for which Calvin claimed the 1961 ?