ChemBark

Here’s one more piquant paper for the file.

I got into a discussion yesterday about chemistry in PNAS and what important papers had been published in the journal. The best I could do off the top of my head was Lewis and Nocera’s review on powering the planet in 2006. After getting dinged from Science and Nature, most chemists seem to turn to Nature Chemistry, JACS, or Angewandte instead of PNAS.

Figuring there had to be something better, I dropped the question on the Twitter feed, and @josarc came through with this gem—a paper by Fred Sanger on DNA sequencing cited a whopping 64,989 times according to Web of Knowledge.

To put that number in perspective, it is almost 1.4 times the total sum of citations for papers by K.C. Nicolaou over his entire career (47,585).

Hot damn. This has got to be the record for chemistry, right?

A kind reader of the blog brought my attention to a piece of commentary in Advanced Synthesis & Catalysis titled “Ethical Conduct in Chemical Research and Publishing”. The lead author of the piece is none other than Ryoji Noyori, who won a share of the 2001 Nobel Prize in Chemistry for his work in asymmetric catalysis. Noyori is the Chairman of the Editorial Board of the journal, while the second author is the Editor of the journal.

I agree with a lot of what Noyori has to say, because a lot of it is obvious:

The research supervisor – group leader, principal investigator (PI), however he or she is called – is the main person to pass on the tradition of science to the next generation. Senior scientists have an obligation to instill strong ethical and moral values in their progeny…However, the education of graduate students should not be the sole responsibility of the research supervisor; each department should have a collective responsibility for the education of its students and for the activities of its professors. It is regrettable to see that in many departments the professors each form their individual kingdoms with a minimum of departmental cohesion.

also:

Fraud is hard to detect in a manuscript and is usually discovered only after publication, if at all. This should lead to retraction of the article.

Yep. The majority of the six-page article is full of statements like the above, which are pretty hard to argue against. But every now and again, Noyori makes some statements that strike me as mostly right, but a little odd:

When the careers of students depend entirely on the relationship to their professor, and only successful results count, then there is a large temptation for abuse on both sides.

I’ll agree that this relationship is very important, but to the point of using the word “entirely”? That’s not an assertion I would make.

It is hard to understand the logic behind committing fraud in spite of the apparent short-term gains. Scientific progress is achieved on the basis of previously published results. Fraudulent results cannot obtain a place of significance in the advancement of science, because they are not reproducible. Therefore, scientific fraud is a suicidal act for the career of the perpetrator. Integrity is an essential requirement for conducting scientific research.

This statement strikes me as naive. I think I understand many of the reasons why people commit fraud, just as I can understand why someone would murder someone else. In both cases, these reasons do not justify the crime, but there is still reasoning and logic at play.

Now, on to two passages that greatly interested me:

Another form of self-plagiarism is to cut and paste large segments of text from previous publications. The case of the Breslow publications offers important insights into the question of self-plagiarism. Ronald Breslow is one of the most highly respected chemists alive, and has made an enormous contribution to chemistry in his distinguished career of over 50 years. He published three personal review articles on the origins of homochirality. Many people are irritated by attacks on Breslow, since it is the right of every scientist to repeat their own ideas in different contexts, especially in talks or review articles. Indeed Breslow was unaware of any misconduct, since he has specifically made changes so as not to infringe on copyright laws. Nevertheless, the invited Perspective in JACS was withdrawn “at the request of the author due to similarity to his previously published reviews..” This is a difficult matter. “Self-plagiarism” can in fact be highly beneficial to the community. Eminent scientists travel worldwide and present almost the same lecture to many audiences; the goal is to have the largest possible dissemination of the ideas and results. The bottom line in publishing similar overviews should be whether it serves the advancement of science by reaching different and larger audiences. Copyright law needs to be respected, but other solutions in the interest of science should be sought to facilitate the widest dissemination of seminal reports. In conclusion, the repetition of a sentence or parts of a sentence is not considered plagiarism or self-plagiarism.

I cannot believe that the top editors of a journal are going to the mat for Breslow’s duplicate publication. I think most editors view the case as a classic example of self-plagiarism that is wholly unacceptable. “Self-plagiarism” is not simply restating your own ideas; it is lifting identical or minimally-altered pieces of writing for re-publication in a new article without clearly indicating that this material was published previously. The reasons self-plagiarism is unethical are: (i) it wastes resources, like the financial resources of the second journal and the time of those scientists assigned to referee material that has already been refereed once before, (ii) it traps the second journal in an adverse legal position with respect to copyright law, and (iii) it uses deception to “game” a system where publications are viewed as the principal metric of accomplishment in research.

And there is a huge difference between giving scientific talks and publishing scientific papers. Justin Bieber can perform “Baby” to audiences in Ottawa, Newark, and Richmond, but he can’t get away with publishing the song over-and-over on subsequent albums under different labels. Noyori’s opinion here is nothing short of bizarre.

If Noyori truly feels that “self-plagiarism can…be highly beneficial to the community”, I suggest that everyone submit self-plagiarized material for duplicate publication in Adv. Synth. Catal. I think he and the other editors will quickly change their tune.

Finally, here is the editors’ requisite thumbing-of-the-nose to blogs:

The Internet has become a major medium of communication in research and is contributing to the democratization of the global science community. Society is conditioned to consider that the printed word is valid; unfortunately, this trust cannot be extended to the Internet. Scientific results put onto the Internet without peer review have a serious problem with credibility. The American Chemical Society guidelines contain a section on publishing outside the scientific literature, but more comprehensive ethical guidelines are needed for publishing in the social media. More harmful is the publishing of irresponsible criticism and slander, even in the blogs of highly respected journals (see the Comments to the C&EN article on Breslow, cited below). Ethical guidelines condemn personal criticism and yet one often sees unscientific accusations, rumor or innuendo in the Internet. The mass media tend towards sensationalism and are not considered scientific, but irresponsible personal accusations on the Internet in an alleged scientific context are damaging to the individuals and to the entire image of science.

What a surprise: the editors of an expensive peer-reviewed journal denouncing the prospect of publishing scientific research for free on the Internet. Also, I love how they criticize “irresponsible criticism” on blogs without specifically citing what they find wrong. They only drop a numbered reference to the web page for the Breslow duplication story at C&EN, which has a comments thread that is heavily moderated by the editors. Someone please identify the slanderous comments that Noyori thinks are so irresponsible. Is this the best he could do?

While the transgressions in the Sames-Sezen and Breslow sagas are very different, we can use both events as probes for how the ACS (through C&EN and JACS) deals with unethical behavior. A lot has changed in the past six years.

The first set of three Sames-Sezen retractions was published in JACS on 1 March 2006. I remarked at the time that these “addition/correction” notices had completely bypassed the ASAP page as well as the daily JACS e-mail feed. This move by the journal may have been unprecedented, and it certainly was not common. The move reeked of sweeping the scandal under the rug. Feeding into this perception was the fact that in spite of the magnitude of the situation, C&EN did not run a story on the retractions until the afternoon of 15 March 2006. Coincidentally—<rolls eyes>—the magazine happened to beat the New York Times to press by a couple of hours. Keep in mind, the ACS Publications division knew these retractions were coming for quite some time, yet once they were finally released, it took an additional two weeks for C&EN to write up a bare-bones story.

In contrast, C&EN ran a story reporting the withdrawal of Breslow’s offending paper less than a day after it was pulled from the JACS site. In both cases: (1) blogs reported the transgressions before anyone else and (2) once the papers were finally withdrawn, online traffic and discussion flared up quickly. The difference this time around was that C&EN did not wait to jump in and provide “official” coverage. It seems that C&EN might have learned a few lessons from 2006: (1) although these stories do not paint chemical research in a positive light, they are important to cover, (2) chemists are interested in these stories, and (3) these stories will not go away, so there’s no sense in waiting to report them.

This apparent change in approach makes sense to me, and I applaud it. In contrast, the editorial decisions made by JACS with regard to retractions—both then and now—are beyond my comprehension.

The recent Breslow perspective was published online and, I assume, in print since it was assigned page numbers (vol. 134, p. 6887-6892). Despite the publication of the paper in print—an action that cannot be reversed—JACS completely pulled the paper from its Web site. The site Retraction Watch noted that it is unusual for a journal to take this step, especially preemptively, before it has completed an investigation. It is more common to leave a copy of the retracted paper online, with a note that refers to its withdrawal. Retraction Watch points to an example where JACS has left a retracted paper online with a notice, and a different example where a paper was retracted and essentially had its DOI commandeered by the subsequent addition/correction notice. The original paper, which had been assigned proper page numbers, now appears as Supporting Information. The case is similar for another JACS article brought into question by the chemical blogosphere: the infamous NaH-as-an-oxidant paper. This paper never made it off the ASAP page—it has no proper page numbers—but it remains online as the Supporting Information for a subsequent retraction notice.

So, what is the pattern? Perhaps we can throw out the Breslow retraction because JACS wanted to avoid liability associated with copyright infringement, but what about the different treatment of the two other retracted papers that made it into print? Odd.

And if we go back to 2006, things get even more strange. Bengu Sezen’s 2004 paper in JACS remains online with a note about the retraction written under the title of the PDF. Fine. But take a look at the addition/correction notice:

After the departure of the first author, the laboratory of the corresponding author (D. Sames) has been unable to reproduce the key results in this publication. Accordingly, the corresponding author withdraws this paper, and deeply regrets that the chemical community was misled by its publication.

Now, look what you’ll see if you open a print edition corresponding to that addition/correction. A kind reader from Montreal sent me a scanned image of the page in question.

After departure of the first author, we were unable to reproduce the key results presented in this paper. The parent coupling between pyrrolidine and iodobenzene does proceed; however, the efficiency is far lower (GC <4%) than originally claimed. The authenticity of spectral data provided in the Supporting Information cannot be confirmed. Accordingly, we withdraw this paper. We deeply regret that the chemical community was misled by this publication.

The two publications are strikingly different. Also, I am not sure whom the “we” referred to in this case. Perhaps that is one reason why Sames and/or JACS decided to make the modification. Whatever the reason, the first version of the retraction completely disappeared from the JACS Web site.

So, in the Breslow and Sames cases, we have situations where the print versions of the Journal are different from the online versions. In the former case, an unfilled hole exists online. In the latter example, the Web and paper editions disagree, and there is no notice of this disagreement.

Why would a journal want to do this? My first thought turns to legal considerations. The original Sames-Sezen addition/correction notices were published under the names of all the co-authors on the paper. We know from Sezen’s comments to the press that she vehemently denied anything was wrong with her work, so she would seem to have a strong claim that she was misrepresented by both Sames and JACS.

But, I don’t know for sure. Everything above is a hot mess, and I don’t think JACS has any firm editorial policy regarding how to deal with retractions. That said, I could easily have overlooked something. Feel free to take me to task in the comments. Regardless, I think many of these actions are inconsistent with one of the central tenets of scientific publishing. Aren’t journals supposed to constitute a permanent record of information? If not, then why can’t we all correct errors we find in our papers by overwriting them online?

You all know that origin-of-life research is near and dear to my heart, and you’re probably sick of how often I lament that the problem has not taken root in chemical academia despite the fact that it almost certainly requires a chemical solution. One of the few PIs at a top university who has dabbled in the field is Ronald Breslow, University Professor at Columbia and a past president of the ACS. Breslow just published this little diddy as a perspective in JACS:

First of all, how often do you see a single-author paper in JACS anymore? It is kind of refreshing. It also means that you can attribute 100% of the content to Breslow, including the ChemDraw structures:

What the hell is that? If I drew that structure on a slide in grad school, my committee would have eviscerated me.

Anyway, let’s get down to the science. Breslow’s premise is that you can take alpha-methyl amino acids found in non-racemic mixtures in meteorites—generated by selective destruction of one enantiomer by circularly polarized UV light—and “use” these compounds to generate non-racemic mixtures of sugars (which are also found as moieties in nucleic acids). Since meteors hit the early Earth with great frequency, maybe one or more of these chiral amino acids was the origin of life’s homochirality. It is an interesting idea and one worth keeping in mind. We could argue all day about how unlikely the scenario is, but this field needs to collect more neat ideas accompanied by simple demonstrations. That said, I take issue with the premise of the paper as outlined in the Introduction:

In 1969 a carbonaceous chondritic meteorite landed in Murchison Australia carrying many organic compounds. These compounds were apparently able to survive the frictional heating as the meteorite passed through our atmosphere since they were initially at ca. 10K, and chondritic meteorites are pieces of rock, with low thermal conductivity, from the asteroid belts that surround the sun. When the meteorite was split open the interior was still cold enough to freeze water.

Among the compounds identified were the amino acids alanine, valine, aspartic acid, glutamic acid, proline, and leucine, which were racemic, with equal mixtures of the L and D forms, along with achiral glycine. However, five amino acids were found that had methyl groups instead of hydrogens on their alpha positions (Figure 1), and these had a range of small excesses of the enantiomers originally described as the L amino acids (in modern terminology they are the S enantiomers). Since that time, these and other α‐methyl amino acids with small excesses of the S enantiomer have been found in the Murchison, Murray, and Orgueil meteorites (ref 1).

The whole point of why the Murchison meteorite is so interesting is that while the “natural” amino acids in it were initially thought to be racemic, subsequent analyses revealed them to have enantiomeric excesses.  I could be missing more recent analyses, but I don’t think so. Breslow should check out these seminal papers (1 2) and revise his background before the paper is “truly” published in JACS.

It is things like the odd ChemDraw structures and completely wrong information in the background that make me question the quality of peer review in JACS (and in all of chemistry, for that matter). I think one should also question the fairness of the editors, for I cannot imagine that this paper would have made it anywhere near publication in JACS if the author were Assistant Professor Joe Schmoe from Sunny Valley Technical College. But that said, the editors of JACS are the sole arbiters of what is “worthy” of publication in JACS, so I’ll just accept it and move on.

Normally, I wouldn’t blog about an otherwise run-of-the-mill paper about the origin of life, but this paper has really taken off in the world of popular science thanks to what amounts to a poetic thought by Breslow used to close the paper:

An implication from this work is that elsewhere in the universe there could be life forms based on D amino acids and L sugars, depending on the chirality of circular polarized light in that sector of the universe or whatever other process operated to favor the L α‐methyl amino acids in the meteorites that have landed on Earth. Such life forms could well be advanced versions of dinosaurs, if mammals did not have the good fortune to have the dinosaurs wiped out by an asteroidal collision, as on Earth. We would be better off not meeting them.

Since you are a reader of blogs, you will recognize this paragraph for what it is: a silly piece of fluff meant to close an otherwise esoteric piece on a humorous note. I’ve got no problem with that. We can argue over whether the joke is funny, but the attempt at humor is obvious…

…except to the staff in the ACS Pressroom, for they issued the following press release to promote the paper. I am copying it here verbatim because these things are intended for distribution—and because it is ridiculous.

Could “advanced” dinosaurs rule other planets?

“Evidence for the Likely Origin of Homochirality in Amino Acids, Sugars, and Nucleosides on Prebiotic Earth”
Journal of the American Chemical Society

New scientific research raises the possibility that advanced versions of T. rex and other dinosaurs — monstrous creatures with the intelligence and cunning of humans — may be the life forms that evolved on other planets in the universe. “We would be better off not meeting them,” concludes the study, which appears in the Journal of the American Chemical Society.

In the report, noted scientist Ronald Breslow, Ph.D., discusses the century-old mystery of why the building blocks of terrestrial amino acids (which make up proteins), sugars, and the genetic materials DNA and RNA exist mainly in one orientation or shape. There are two possible orientations, left and right, which mirror each other in the same way as hands. This is known as “chirality.” In order for life to arise, proteins, for instance, must contain only one chiral form of amino acids, left or right. With the exception of a few bacteria, amino acids in all life on Earth have the left-handed orientation. Most sugars have a right-handed orientation. How did that so-called homochirality, the predominance of one chiral form, happen?

Breslow describes evidence supporting the idea that the unusual amino acids carried to a lifeless Earth by meteorites about 4 billion years ago set the pattern for normal amino acids with the L-geometry, the kind in terrestial proteins, and how those could lead to D-sugars of the kind in DNA.

“Of course,” Breslow says, “showing that it could have happened this way is not the same as showing that it did.” He adds: “An implication from this work is that elsewhere in the universe there could be life forms based on D-amino acids and L-sugars. Such life forms could well be advanced versions of dinosaurs, if mammals did not have the good fortune to have the dinosaurs wiped out by an asteroidal collision, as on Earth. We would be better off not meeting them.”

What. The. Hell. Some booger-eating PR guy on 16th Street jumped to the end of the manuscript and took Breslow’s joke at face value. Then, his/her editor never thought to question the idea, and sent the press release out in the weekly PressPac. Now, the ACS is the laughing stock of the world of scientific publishing and popular science writing.

I guess we’ve learned nothing from the NASA/Wolfe-Simon/Arsenic Life episode. Why the hell do these things always seem to happen to origin-of-life chemistry?

:/

See also:

Just Like Cooking
Chemistry-Blog
Pharyngula
David Bradley’s Sciencebase
The Awl

This article from 1965 might be the first example of the publication of a purely farcical chemistry paper in a respectable journal. This article also appears to have completely eluded the attention of blogs, most likely because bloggers were especially lazy in the 60s. The unmistakable quality of the paper is certified by a consequent letter to the editor, in which a concerned member of the Canadian Medical Association wrote:

I was appalled to read J.S. Greenstein’s Very Original Article on “Armpitin”…I am very sorry to observe that the official journal of Canadian doctors has published this article.

The paper describes the development of armpitin as a powerful contraceptive agent. While the author provides a structure for a portion of the molecule, he refuses to provide the full details of its synthesis because he “intends to make a fortune.”

The results seem unsurprising. I would wager that a majority of us have collected anecdotal evidence that a repetitive string of NOs can be very effective at preventing pregnancy. The author reports he serendipitously stumbled into the field of contraceptives while designing deodorants. One deodorant led to a noticeable increase in libido without concomitant increase in pregnancy. His initial studies proceeded from there:

With typical male self-assurance, we undertook to examine the females for the causative factors leading to their infertility. We employed every known gross anatomical, histological, histochemical, biochemical, endocrinological, physiological and psychological test of reproductive capacity and could find no evidence of malfunctioning of the female reproductive systems and accessory structures. We could only conclude, reluctantly, after months of exhaustive investigation, that the females were normal in all respects, and that we should turn our attention to the males.

When we took the trouble to examine the ejaculates obtained by masturbation, artificial vagina, or by post-coital recovery from the site of deposition, the answer to the enigma stared back at us through the narrow barrel of the microscope tube: THERE WERE NO SPERMATOZOA IN ANY OF THE SEMEN SAMPLES.

Yeah, this paper was actually published in a respectable journal—and in 1965, when by all accounts, people were humorless. (There is simply no other rational explanation for the popularity of Jerry Lewis.) What shocks me more than anything is that the content of the paper is 98% pseudo-legitimate technobabble and only 2% punchlines, yet the editor allows the damn thing to go on for 5 pages. That said, the list of references is particularly amusing. The author acknowledges “A. Gabriel” for divine inspiration in the form of a personal communication, and also cites a paper on orgasm by C. Men as well as a child’s guide to erotica by M. Goose.

While I regularly advocate that Carl Djerassi should be recognized by the Nobel Committee, I don’t think that Dr. Greenstein’s seminal contribution rises to the same level.

Yesterday, I attended an interesting symposium that featured a slate of talks by five undergrads here at Caltech. During a presentation on the formation of dendritic structures during the recharging of lithium batteries, I was momentarily distracted by a citation to the following paper:

 Kahanda, G.L.M.K.S.; Tomkiewicz, M. J. Electrochem. Soc. 1989, 136, 1497.

That has got to be a record for the chemist with the most middle names. His full name—which can be found in his Ph.D. thesis on the electrochemical morphogenesis of zinc and silver—is Galathara Lekamge Mahendra Kumara Samarakone Kahanda. Remarkably, it appears that he is related to a computer scientist with an even longer name: Galathara L.A.U.K.S. Kahanda. Well, either that, or he found a two-for-one deal and traded in his “M”.

You think these guys know Govindjee?