Sunday, April 25, 2010

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 Biology-Online.Org's Forum

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

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 hydrogen.  And last, but not least this triose called glyceraldehyde phosphate 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 Melvin Calvin, 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 carboxylation 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 molecule of PGA (phosphoglycerate) and the other a triose, glyceraldehyde phosphate, which condenses to make glucose and, then, starch. 

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 Carbon 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 water and carbon dioxide 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 molecules of the 3-carbon D-glycerate-3-phosphate, 3-PGA.


With the "high-energy phosphoanhydride bonds" in the ATP, adenosine triphosphate, 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 →→→ Sucrose          (L)
                                          |                                                  
                                          ──> 3-PGA

                     RuBP + CO2  ────> 3-PGA + 3-PGA                   (D)


                      RuBP + 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 enzyme (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 carbon fixation 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 Chemistry 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.


C. 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 Physical Chemistry 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 activity reported 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 stroma," as follows cooperates with the light reactions "in the thylakoids,"  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 carbon cycle 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 on the right) 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."


D. 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, Photosystem I ("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.


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 Nobel Prize in Chemistry?


    Sunday, April 11, 2010

    Patterned Activity : Six Decades of the Calvin Cycle's Dominance

    For the National Science Foundation's explanation backed by members of the National Science Board of how the Calvin cycle was established contrary to Calvin et al's finding of the light carboxylation reaction, please visit the Calvin Cycle Website.

    The author Francis K. Fong back in the late 1950's discovered the Calvin cycle, Mother Nature's dark reaction cycle, her formula for doing chlorophyll photosynthesis in the light in the dark.  He has since been in pursuit of a resolution for the improbable phenomenon.   

    A potential solution came in the form of Cordova's finding, that a search on the Web of Science using "dark reaction cycle AND photosynthesis" came up with not a single result.  The inquiry is, whether Cordova's finding is tantamount to a conclusion that the federal funding of photosynthesis research predicated on the Calvin cycle is a tax-related conspiracy. The focus here, for purposes of Fong's report to Bobby Hunt (IRS EXEC), is whether the patterned activity reported in Hunter's complaint is responsible for the making and maintenance of the Calvin cycle over the sixty years of its dominance.

    Fong is authorized, under a statutory contract with the U.S. Treasury, see, Rev. Agt. Hunt Jr.'s Submissions, to detect and bring to trial members of the bribery-conspiracy for PCDF's promotion of the Lawler tract, who come from different walks of life. The instant detection of the Calvin cycle as a tax-related conspiracy is specialized to members of the dark photosynthesis community taking advantage of PCDF's agreement with Melvin Calvin for making of the dark reaction carbon cycle, NSF's Dark Photosynthesis Funding Scheme.

    Of the practitioners of the Calvin cycle there are two categories: officers of the United States acting in connection with the internal revenue statutes and persons who are not employed by the United States.

    The criminal tax statutes in Title 26 of the United States Code do not include a statute for the crime of conspiracy. Tax-related conspiracies are generally prosecuted under 18 U.S.C. § 371, the general conspiracy statute. Section 371 sets out two types of conspiracies. United States v. Helmsley, 941 F.2d 71, 90 (2d Cir. 1991), cert. denied, 112 S.Ct. 1162 (1992); United States v. Arch Trading Co., 987 F.2d 1087, 1091 (4th Cir. 1993).

    Conspiring or agreeing to engage in conduct, which is prohibited by a substantive Title 26 offense, is a prosecutable offense under Section 371.

    Section 371 may also be violated by conspiring or agreeing to defraud the United States, meaning, “primarily, to cheat the Government out of property or money,” and also, “interfere with or obstruct one of its lawful governmental functions by deceit, craft, or trickery, or at least by means that are dishonest.” Hammerschmidt v. United States, 265 U.S. 182, 188 (1924).

    In addition to Section 371, for employees and officers of the United States, acting in connection with any revenue law of the United States, 26 U.S.C. § 7214(a)(4) contains a provision prohibiting conspiracy to defraud the United States.  See, United States v. Eisenmann, 396 F.2d 565 (2d Cir. 1968).

    In addition to a charge of murder, or conspiracy to commit murder in aid of Posner's order of the MacLauchlan contract, a felony, an offense by an individual or organization to cheat the Government out of property or money subjects the offender to the Criminal Fine Enforcement Act of 1984 (P.L. 98-596) enacted 18 U.S.C. § 3623. Where 18 U.S.C. § 3623 is applicable, which was changed to 18 U.S.C. § 3571, commencing 11-1-86, the maximum fine under 18 U.S.C. § 371, for felony offenses committed after 12-31-84, would be at least $250,000 for individuals and $500,000 for corporations.

    Pertinent to the offenses committed in furtherance of the Calvin cycle, Fong contemplates the application of the alternative provision, 18 U.S.C. § 371 (d), as follows.  If any person derives pecuniary gain from the offense, or if the offense results in a pecuniary loss to a person other than the defendant, may be fined not more than the greater of twice the gross gain or loss.

    The offense in furtherance of the Calvin cycle is likely to result in pecuniary losses to the United States, or Fong, in excess of tens of billions of dollars.

    Back to the Calvin Website.

    Wednesday, April 7, 2010

    Fong's Demonstration of the Chlorophyll Water-Splitting Reaction : Kamen on Origins of the Calvin Cycle - Asilomar Meeting with Melvin 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."  - Melvin Calvin's advice to the author Francis K. Fong on the establishment of the Calvin cycle, Asilomar CA, 1978.  

    "You are a brave man to stir such a big pot all at once.  I will be interested to see where the bodies will lie."  -- Andrew A. Benson, Letter of 5-22-81 to Francis K. Fong; see, Fischer's Public Letter.

    "Dr. Siedow and his reviewers did not have fraud in mind [and] may have been negligent in that they did not read the original publications by Calvin et al as quoted by Dr. Fong in DCB 8822928." -- National Science Foundation's explantion of its flawed rejection of Fong's NSF Proposal No. 8822928 on NSF funding of photosynthesis research based on the Calvin cycle as a federal false claim.  See, NSFfunding.com's Synopsis site.  The explanation resulted in the murder of Don MacLauchlan, vice-president of Carbon Reduction, sponsor for DCB 8822928.


    Fong and Calvin's Discussion at Asilomar

    Francis K. Fong's discovery, in 1976-79, of the water splitting reactions in photosynthesis, in vitro, using a single, red-light activated chlorophyll photosystem resulted in his DOE-sponsored meeting with the late Melvin Calvin at the Asilomar Conference in 1979.  Here, the author recounts the day-long discussion, which closed with an explanation why Calvin cultimately abandoned his research on photosynthesis to focus on growth of sugarcane plants in Brazil.   

     



    Fong, left, and Calvin discuss the Calvin cycle and red-
    light Chl a carbon-reduction in meeting arranged by DOE


    This discovery was was motivated by yet another discovery, that of Fong's uncovering, while in search of an undergraduate thesis topic in 1958-59, of the Calvin cycle attributed to Calvin.


    The demonstration in vitro of red-light activated water splitting reactions using a single chlorophyll system is important. Proponents of the dark reactions in photosynthesis argue that a single chlorophyll photosystem does not support sufficient "emf at pH7" to split water and reduce carbon dioxide photochemically. The demonstration proves otherwise.  Light energy is measured in electron volts, not emf's.  The latter is a unit, a thermodynamic quantity, having nothing to do with photochemistry.  Proponents of the Calvin cycle would have a Z scheme of two light reactions with sufficient emf's to produce NADPH (the reduced form of NADP+, nicotinamide adenine dinucleotide phosphate) and stored chemical energy (of the "high-energy phosphoanhydride bonds" of ATP, adenosine triphosphate) for reducing, in the dark, carbon dioxide to the sugar oxidation level. 

    Fong's uncovering of the Calvin cycle, the dark reactions in photosynthesis, is important.  Calvin discovered, not the dark reactions, but the reaction (L) - a reductive carboxylation reaction in photosynthesis that occurs only in the light.  The discussion at Asilomar focused on the question, why did Calvin keep silent all these years, when he received the Nobel Prize for that light reaction discovery and, then, allow the community to believe that he accepted the high honor for something as unreasonable as "dark photosynthesis"?
     
    Fong's uncovering of the Calvin cycle: From left,
    Melvin Calvin and Andrew Benson (1954), the author
    (1959) and J.A. Bassham.  In his letter to Fong.
    Benson persisted in believing that carbon reduction
    is a dark reaction cycle: In 1954 he was dismissed by
    Calvin from Berkeley's Radiation Lab.  As a
    result he was unaware of the subsequent development
    of the reductive carbon reactions in photosynthesis.
    Calvin's rejection of carbon fixation as a dark reaction in photosynthesis is well-documented.  In the late 1940's Andrew Benson of his lab was a strong proponent of photosynthesis as a dark reaction cycle.  See, e.g., Wikipedia's one and only reference to the original literature in its representation of the Calvin cycle: 
    Bassham J, Benson A, Calvin M (1950). "The path of carbon in photosynthesis". J Biol Chem 185 (2): 781–7. PMID 14774424. http://www.jbc.org/cgi/reprint/185/2/781.pdf.
    In 1958-59, Fong discovered the Calvin cycle, the dark reactions in photosynthesis, in that it was contrary to the original papers by Calvin et al from 1952 on.  At about that time, in the final paper of Calvin's series of C-14 tracer studies, Calvin & Pon (1959), J. Cell. Comp. Physiol., 54, Suppl. 1, at 65-67, Calven concluded that RuBisCO, ribulose-1,5-bisphosphate carboxylase-oxygenase, is possibly not the enzyme 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." 



    Finally, a year later, Bassham, J.A. and Kirk, M. (1960) Biochim. Biophys. Acta, 43, 447-464 independently confirmed Calvin's finding of the photo-reductive carbon fixation reaction in photosynthesis.  (For a review of Calvin's original papers on the Berkeley group's finding of the carbon-reduction light reaction, see, NSFfunding.com's Calvin cycle page.)  Concluded Calvin in his Noble Lecture, Calvin, M. (1964) at 638:
    "Here the intermediate is split by hydrolysis to two molecules of phosphoglyceric acid. However, in our earlier work the possibility of a reductive fission at the same point to give one molecule 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."


    Accordingly, 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 and one molecule of PGL, glyceraldehyde phosphate, a triose. Calvin's reductive path of carbon is reproduced below.

    Calvi's conclusion of the light carboxylation reaction in photosynthesis, Calvin, M. (1964) at Fig.20.

    How and why, then, was the Calvin cycle established contrary to Calvin et al's finding of the light carboxylation reaction in photosynthesis?

    The extensive, day-long discussion proved uneventful, except that Calvin turned on Purdue's formation of the PCDF, conceding that the questions as to Fong's discovery of the Calvin cycle were among the reasons for the Berkeley group's turning its research focus on the growth of sugarcane plants in Brazil.  

    The Asilomar meeting concluded with what appeared to Fong was Calvin's expression of deep regret, when he mumbled with a soulful sigh, "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." 

    Barbara J. Garrison Festschrift

    For the NSF's explanation of a second-year university level biochemistry approach to understanding how the Calvin cycle was established contrary to Calvin et al's finding of the light carboxylation reaction in photosynthesis, please visit NSFfunding.com.


    On this post the author Francis K. Fong gives an account of his discussion with the late Melvin Calvin at the Asilomar conference on Fong's discovery of the Calvin cycle.  That discussion led to Martin Kamen's recollections on how photosynthetic carbon fixation as a reaction in the dark came about in 1941.  It is, of course, well-established in reputable journals that Calvin et al in their celebrated C-14 tracer work found the light carboxylation reaction in photosynthesis.  For the story of how the Calvin cycle became established as a fraud, see Fong's 4-25-10 post, Cordova's Finding, on this blog.   



    Here, Fong corroborates Purdue University President France Cordova's finding unraveling his discovery in 1958-59 of the Calvin cycle, the dark reaction in photosynthesis.  The story of that discovery picks up 20 years later at NSF Biophysics Program Director Martin Schweizer's invitation for Fong to submit a workshop proposal. The need existed to assess the meaning of the dark reaction cycle in light of the 1976-79 experiments described below.  A meeting involving Fong and Calvin took place as a result at the Asilomar Conference sponsored by the Energy Department. 



    Journal of Physical Chemistry C Barbara J. Garrison Festschrift
    April 1, 2010, Volum 114, Number 12 (Click here for Larger Size).


    Thirty more years elapsed.  Then, but for a serendipitous occurrence, an unrelated decision of the editors of the Journal of Physical Chemistry C, nothing noteworthy of the Asilomar meeting would have survived the ravage of time.  The JPC C editors' decision was to publish, in the spring of 2010, a special issue in honor of Barbara J. Garrison.  As it turned out that decision led to Fong's reconstructing, with the help of John Grutzner and Purdue President France Cordova, the years of discovery, 1974-1979, which overlapped Garrison's tenure at Purdue.  That reconstruction was heightened by Cordova's finding of 2-1-10, prompting Fong to contemplate a determination whether that finding is tantamount to a conclusion that NSF funding based on the Calvin cycle was a result of the patterned activity disclosed by Beering.      

    Fong's Water-Splitting and Carbon-Reduction Reactions

    In 1976-79 Fong and co-workers demonstrated the chlorophyll photochemical reactionss in vitro(1-3) in corroboration of Wilson and Calvin’s observation in vivo (1955),(4) in support of a reductive carboxylation reaction in photosynthesis, in which the carbon is directly reduced in the light to the sugar level, contrary to Bassham et al's suggestion of a reaction cycle in which the carbon is not reduced.(5)


    The 1976 photogalvanic experiment
    (For a recent photo, click here.)

    (1) "In Vitro Solar Conversion after the Primary Light Reaction in Photosynthesis. Reversible Photogalvanic Effects of Chlorophyll-Quinhydrone Half-Cell Reactions," Fong, Francis K. and Winograd, Nicolas (1976) J. Am. Chem. Soc., 98, 2287.
    (2) *"The Primary Water Splitting Light Reaction. Mass Spectrometric Determination of Gaseous Hydrogen and Oxygen Evolution from Water Photolysis by Platinized Chlorophyll a Dihydrate Polycrystals," Fong, Francis K. and Galloway, Lory (1978) J. Am. Chem. Soc., 100, 3594-3596.
    (3) *“Photosynthesis of Polyatomic Organic Molecules from Carbon Dioxide and Water by Photocatalytic Action of Visible Light-Illuminated, Platinized Chlorophyll a Dihydrate Polycrystals," Fruge, Daniel R., Fong, G.D., and Fong, Francis K. (1979) J. Am. Chem. Soc., 101, 3694-3697.
    (4) Wilson, A.T. and Calvin, M. (1955) J. Am. Chem. Soc., 77, 5948-5057.
    (5) Bassham, J.A., Benson, A.A., Kay, L.D., Harris, A.Z., Wilson, A.T., and Calvin, M. (1954) J. Am. Chem. Soc., 76, 1760-1770.


    The 1978 water-splitting reaction
    Showing the red photoreactivity

    In 1981 the NSF published in Mosaic a story on Fong’s finding on the photosynthetic water splitting reaction. The premise was, "others who have tried" were unable to produce the results reported by Fong. Shocked by its implications, Purdue University conducted an extensive investigation. In 1986, the University administration acknowledged an NSF site visit team's finding that Fong, indeed, was the first to have demonstrated in vitro the chlorophyll water splitting. The recognition resulted in the formulation of the Fong-Butcher model, which Beering, in sworn testimony, vouched for as “correct ***, upheld and indeed any questions *** removed.” Beering is Chair of National Science Board (NSF) overseeing NSF's operations.

    Significantly, all Fong's theoretical and experimental work at Purdue and NSFfunding.com corroborated Calvin and co-workers' C-14 tracer studies. Those studies are all but forgotten on account of the Calvin cycle, notwithstanding Beering's sworn testimony backed by the Estonian group Eichelmann and Laisk (1999), who explained the results reported by Laisk et al (1987) in terms of Fong and Butcher (1988). Laisk's group is a bedrock of the dark photosynthesis research community.

    Gathering of 1978 : Kamen on Origins of Dark Photosynthesis

    To celebrate the occasion of Fong's finding of the chlorophyll water-splitting reaction, Martin Kamen, co-discoverer (1940) of the long-lived carbon isotope 14C that enabled the tracer studies at Lawrence Radiation Laboratory (LRL), Felix Haas, Purdue School of Science Dean (later Provost), and Nobel Laureate Herbert C. Brown celebrated Fong's 40th birthday.


    During dinner, Kamen recounted the accidental death (1943) by phosgene poisoning of Sam Ruben, who during the war years worked on elucidating the deadly properties of phosgene samples 11C-enriched by Andrew Benson. In collaboration with C. B. van Niel of Stanford University, Ruben and Kamen pioneered the concept that reduction of CO2 in green plants could occur in the dark, in a process akin to bacterial (non-chlorophyllous) systems. Dark plant photosynthesis was born.
    Referring to Ruben’s genius and LRL workers’ finding after his death of the photoreductive path of carbon,4 Kamen said: “Had Sam lived, he would have reached the conclusions you have. Take care of yourself; we need you to make your [chlorophyll water-splitting] discoveries count.”

    Gathering of 2008



    On August 2, 2008, Fong, his wife, Margareta, and their friends, John Grutzner, Dennis Diestler, Barbara Garrison, Jocelyn Grutzner and Nick Winograd, gathered in Pittsburgh for a weekend of celebrations of Fong's 70th birthday, which douled for the 30th anniversary of the chlorophyll water splitting reaction.   

    On 12-21-09, Leo Zhigilei, Winograd's co-editor for an upcoming special issue of the Journal of Physical Chemistry C in honor of Garrison, wrote Fong a letter. The editors were working on a biosketch of Garrison for this issue. Would Fong be willing to write something about her tenure at Purdue?

    Winograd's Chlorophyll Photogalvanic Reaction : The Asilomar Meeting with Melvin Calvin on the Calvin Cycle

    The Asilomar meeting with Calvin.  Garrison's tenure at Purdue spanned the years of discovery, 1975-1979.  Fong's vague memories of them were as follows.  They were a stormy period for Purdue's chemistry department. In or about 1977 Martin Schweizer, NSF Biophysics Program Director, invited Fong to give a lecture at NSF on Nick Winograd's demonstration of the chlorophyll a dihydrate photogalvanic effect, which was later shown to be a manifestation of the water-splitting reaction.  Schweizer asked Fong to submit a workshop proposal to advise NSF on its standard for funding dark photosynthesis research.

    At about the same time, Energy (DOE) Deputy Energy Research Director Doug Pewitt sent Fong to observe Lawrence Radiation Laboratory workers at Asilomar, California. There Fong visited with Calvin, then head of LRL Chemical Biodynamics. Given that Calvin and Fong both knew photosynthetic carbon reduction, in vitro or in vivo, was neither dark nor cyclic, they discussed the origins of the dark photosynthesis reaction cycle. The discussion led to Calvin's explanation of LRL’s switch from researching the chlorophyll water-splitting to the growth of banana trees, turning on Purdue's formation of the PCDF for him to establish the Calvin cycle.


    Calvin concluded the meeting at Asilomar with the warning: "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."

    Zhigilei's inquiry.  At the time of the Asilomar meeting, Fong was charged with building the national standing of the physical chemistry division. In that capacity he became engaged in many discussions involving Purdue's administrative ranks, when Penn State made strong bids to hire Garrison and Winograd away from Purdue. Zhigilei's inquiry provided the occasion to reconstruct those early years. What happened then resulted not only in Garrison and Winograd's departure for Penn State, but also the turnovers in Purdue's administration in the decades which followed.

    Grutzner's Communication of Calvin-Pon

    Fong responded favorably to Zhigilei's inquiry, after he was assured of Grutzner's assistance to document the causative factors underlying the transitions in Purdue's administration. In early January of 2010, Grutzner emailed a pdf file of the 1959 paper by Calvin and Pon (1959), in which Calvin summarized Berkeley Lawrence Radiation Laboratory workers' finding of the photoreductive carboxylation reaction.  Grutzner's communication of Calvin and Pon was the catalyst for bringing about Cordova's finding. 

    On 1-15-10, Fong submitted two versions of his "Tribute to Barbara Garrison." Realizing that Zhigilei requested a "short story," Fong reproduces here, in its entirety, the longer version reviewed by Winograd, in which Fong described in detail the devastating effects of Calvin-Pon on Purdue's chemistry department.  In the parts relevant to this webpage, Fong wrote:

    • "I went over with Calvin [in the Asilomar meeting] a literature survey of dark photosynthesis research. In 1941, Ruben and Kamen (Berkeley) in collaboration with van Niel (Stanford) advanced the concept that reduction of CO2 in plants could occur in the dark, in a process akin to bacterial (non-chlorophyllous) systems. In 1954, dark photosynthesis, or reductive carboxylation in the dark, was thought to have been experimentally established by Calvin et al as a cyclic reaction. Even so, as early as 1952, Calvin and Massini proposed a possible mode of photoreductive carboxylation, when they first recognized the carboxylation of ribulose bisphosphate (RuBP); thereafter, from 1955 on, Calvin et al's 14C-tracer studies yielded but one result, that carbon reduction in vivo is neither dark nor cyclic.

    • "'Why, then, did you go on to accept the 1961 Nobel Prize for the dark carbon reduction cycle?' I asked. Calvin’s response was shocking; he said something like, 'I accepted the Nobel Prize to honor Purdue’s 1955 news release, reporting that I demonstrated in vitro the dark reaction cycle contrary to what we reported in Wilson and Calvin (1955). In all my papers from Wilson on I told the truth. I told the truth in the Calvin-Pon paper of 1959.' So Calvin told the truth in his papers, but received the Nobel Prize on an untruth distributed by Purdue?

    • "[***] The Purdue management ranks were in disarray as a result of Calvin’s input of Purdue chemistry’s release of the incorrect 1955 Chem. Eng. News story. Armed with that story, I dug up the Calvin-Pon article and confronted the then chemistry department head with it. Calvin-Pon was Calvin’s final experimental paper on the subject of reductive carboxylation. In it, he truthfully reported that, 'by more-precise measurements of the rate of approach to C-14 saturation of the pools of PGA and ribulose diphosphate (RuBP) in algae and in a more nearly true steady state of photosynthesis than has heretofore been achieved,' LBL workers obtained 'the best evidence' of their conclusion dating from Calvin and Massini (1952) that reductive carboxylation occurs in the light, a non-cyclic reaction, in which CO2 uptake (by the RuBP) results in reduction of one half of the 6-carbon adduct directly to the sugar level. Calvin and Pon concluded that the observed reductive splitting 'might very well require a reducing system as yet unknown.'

    • "The department head, who happened to be the person responsible for distributing the 1995 Chem. Eng. News story, was single-handedly responsible for misleading the government in funding dark photosynthesis and was, therefore, unable to support Martin Schweizer’s request for me to submit a workshop proposal."

      The conclusion was shocking.  The Calvin cycle, the dark reaction cycle in photosynthesis, had nothing to do with photosynthesis!

      Diestler's Reactive-Complex Theory

      In the winter of 1975-76, Fong published a review on the collaborative development by Diestler, Karl Freed (The James Franck Institute, University of Chicago) and himself of a quantum statistical mechanical (QSM) approach as a successor to the transition-state theory. Shortly thereafter, Garrison and Diestler used the Montroll-Shuler model for the kinetics of diatomic molecular dissociation adapted to thermal desorption of gases from solid surfaces, again in comparison with that predicted by transition-state theory. In the course of this research, Garrison and Fong developed a close relationship discussing their respective approaches to chemical rate theory. Fong may have provided her with the kind of feedback and support lacking from her productive but otherwise turbulent postdoctoral experience. At the same time, during their many informal discussions, Garrison made insightful suggestions that led Diestler and Fong to invoke the Born-Oppenheimer adiabatic approximation to formulate a nonequilibrium theory of chemical rate processes in condensed media. In this theory, the photo-excitation of a “reactive complex” may result in either deactivation to the ground state or reaction to yield the primary photochemical products—a model for the primary photochemical reaction in chlorophyll photosynthesis, which eventually developed into the Fong-Butcher model for photoreductive carboxylation in photosynthesis.