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Aug 07

When Authors Forget to Fake an Elemental Analysis

by mitch | Categories: science news | (79300 Views)

Reto-Dorta

As first posted by ChemBark, a recent paper in Organometallics by Professor Reto Dorta at the University of Zurich is catching the ire of the online chemical community today [, ] for a quick throaway note left in the supporting information in the paper entitled, “Synthesis, Structure, and Catalytic Studies of Palladium and Platinum Bis-Sulfoxide Complexes“. On page 12 of the supporting information a note is left for the first author Emma E. Drinkel*, presumably by Reto Dorta, saying, “Emma, please insert NMR data here! where are they? and for this compound, just make up an elemental analysis…”.

Emma Drinkel Note

The full supporting information file is attached for your reference. Supporting information for: Synthesis, Structure and Catalytic Studies of Palladium and Platinum Bissulfoxide Complexes

Update 1: Letter from the Editor and Chief of Organometallics

gladysz

Wednesday 07 August
Dear Friends of Organometallics,

Chemical Abstracts alerted us to the statement you mention,which was overlooked during the peer review process, on Monday 05 August. At that time, the manuscript was pulled from the print publication queue. The author has explained to us that the statement pertains to a compound that was ”downgraded” from something being isolated to a proposed intermediate. Hence, we have left the ASAP manuscript on the web for now. We are requiring that the author submit originals of the microanalysis data before putting the manuscript back in the print publication queue. Many readers have commented that the statement reflects poorly on the moral or ethical character of the author, but the broad “retribution” that some would seek is not our purview. As Editors, our “powers” are limited to appropriate precautionary measures involving future submissions by such authors to Organometallics, the details of which would be confidential (ACS Ethical Guidelines, http://pubs.acs.org/page/policy/ethics/index.html). Our decision to keep the supporting information on the web, at least for the time being, is one of transparency and honesty toward the chemical community. Other stakeholders can contemplate a fuller range of responses. Some unedited opinions from the community are available in the comments section of a blog posting: http://blog.chembark.com/2013/08/06/a-disturbing-note-in-a-recent-si-file/#comments

If you have any criticisms of the actions described above, please do not hesitate to share them with me. Thanks much for being a reader of Organometallics, and best wishes,

John Gladysz

Editor-­in­‐Chief

Update 2: Reto Dorta allegedly responds by email to Sufi.

reto-dorta2

Dear Sufi,

Thank you for your e-mail.

Compound 14 in the SI is an intermediate and has not been fully characterized, hence does not have a number in the manuscript. Wording and numbering of the compounds in the supporting information are wrong (on different levels!). Characterized compound 14 and 15a-c of the article correspond to compounds 154, 165a, 165b and 165c of the supporting info.

Anything else is being dealt with by the editors of the journal as we speak.

Best regards

Reto Dorta

Update 3: Carmen Drahl and Stephen K. Ritter report in C&EN:

blog-drahl

TL;DR Organometallics editor Gladysz told us that Dorta told him that the “just make up” statement was inappropriate. Also, the now-infamous SI was an earlier version uploaded to the journal servers at the point of submitting corrections. Reviewers saw another version.

Update 4: John Gladysz, Chief Editor of Organometallics, leaves a very detailed response on Paul’s blog.

john2

I have been meaning to contribute a post to this blog, where there has been so much good dialog involving the Reta Dorta manuscript on the ASAP site of Organometallics (om-2013-00067 or DOI: 10.1021/om4000067). There have been hits and misses, but I’d like to thank everyone for all input and commentary. Although I write this sentence with a wink to all my friends on my masthead page (http://pubs.acs.org/userimages/ContentEditor/1219929142245/orgnd7-masthead.pdf), this has made me muse whether an Editor-in-Chief could dispense with a high-maintenance Editorial Advisory Board and simply throw the various thorny issues that arise out for adjudication on a quality blog like Chembark.

I’ll attempt to address some of the many good points raised in a series of posts. I can’t promise I can reply to any counterpoints (e mail traffic has been heavy and will likely remain so), but I’ll be sure to read them.

A lot of comments have been made about the breakdown of the peer review process in this particular instance, and if you read to the end of this post you will get some specifics, within the confidentiality bounds that I am obliged to maintain as an Editor. However, you are going to have to bear through a general analysis of the many things that can go wrong with SI first.

The first vulnerability is in the initial submission. I don’t want to put down coauthor written manuscripts, but there are some corresponding authors who have clearly never laid an eye on their SI. Without this check, and I’m talking about a word-by-word read with attention given to every reagent quantity, spectroscopic data point, significant digit cutoff, etc., major errors are much more likely to slip through. My research group uses a proofing checklist, with every author fully participating, crystallographers excepted (except for their sections).

The second vulnerability is with the referees. I want to comment that I consider the pool of reviewers used by Organometallics as extremely conscientious. But obviously there will be cases, with any journal, where the SI is neglected.

A relevant digression involves JACS manuscripts. A reviewer may decide that the manuscript does not meet certain breadth/urgency criteria, and therefore not critique the SI. When such manuscripts are resubmitted to Organometallics (often with copies of the JACS reports), we do not render an Editorial decision until we are confident that the entire manuscript has been thoroughly peer reviewed.

The third vulnerability is with the Editors. I do not expect my Editors to carry out a word-by-word examination of the SI. However, we do follow an internal check list that I could in principle share, but all of the points therein can be found in our “Author Guidelines” (http://pubs.acs.org/paragonplus/submission/orgnd7/orgnd7_authguide.pdf)

An attendant vulnerability, pointed out by several on this string, involves the submission of the revised manuscript and accompanying SI. Suppose a reviewer or Editor requests that a melting point be added. At this stage, the Editor is unlikely to check anything other than the relevant paragraph. If an author has introduced other errors by some means (many comment about fixing minor typos), these will be overlooked.

In summary, it is necessary to look at error introduction from a number of perspectives, and it may be difficult for “younger” authors with less publishing experience to view things from the inside. I’ll eagerly “steal” any substantive additions that anyone offers if I ever have to present this analysis again, or incorporate it into a future Editor’s Page of Organometallics.

There are other things that can be done to reduce errors. When I did my major rewrite of the “Author Guidelines” that I inherited from my predecessor, I stole an idea from Dale Poulter at J. Org. Chem. and more or less required that all experimental data be reported in the main text of full papers. This excerpt is from section 4.3.8:

“For Articles and Notes, the bulk of the experimental section should be presented in the main text. Supporting Information should only be used to describe the syntheses and characterization of new compounds of subordinate interest: for example, the preparation of an isotopically labeled species by an otherwise known procedure or a salt with an alternative counteranion. Characterization data for known organic compounds prepared using a new catalyst would also be appropriate for Supporting Information.”

When om-2013-00067 was submitted, the experimental section (including all compound syntheses) was in the main text and the referees did exemplary jobs. One commented among other remarks “There is a fair amount of work in this paper, however 51 pages is definitely too much so downsizing the article would be appreciated especially as the relevance of the work is lost in the size of the article”. Neither the reviewer nor the processing Editor in his response recommended moving any content to SI. However, the author, in a not illogical attempt at accommodation, replied to reviewer 2 as follows: “We have shortened the article by taking away …. We have also incorporated all experimental data into the supporting information.” Exceptions are sometimes allowed to our policies, and in the processing Editor’s judgment it was more appropriate to honor the reviewer recommendation than adhere the protocol in section 4.3.8 of the Author Guidelines. Most Editors, including myself, would assume that a straight up cut/paste transfer between two documents could be competently carried out. However, this was not checked and nothing was returned to the referees, so the rest is history.

As noted above, additional posts may follow if time allows.

May your chemistry be highly successful, and may you execute it thoroughly and write it up in such a way that it can forever stand the test of time.

Best wishes,

John Gladysz
(on whose desk “the buck stops” for everything, good and bad, at Organometallics)
(for non-native speakers: http://en.wikipedia.org/wiki/Buck_passing)

Update 5: John Gladysz goes into extraordinary detail on what to do when a product is solvated [null]. Provides a handout: Solvates: Avoiding Common Errors

There has been due attention given to the microanalytical data in the Dorta manuscript and Drinkel thesis in this string.

Personally, the first thing first caught my attention was that both documents report identical reactant quantities, identical reaction conditions and workups, and identical product quantities and yields for the four compounds highlighted in the ChemBark post. However, the products are represented as solvated in the thesis, and unsolvated in the manuscript.

This of course cannot be, and is issue I want to focus on in this comment.

First, I’m a stickler for reporting both mass (typically g or mg) and molar (mol or mmol) quantities of all products (just as one does for reactants), not just the yields or yields and masses. I recognize that yields/masses only is a common format today, but this was not case some decades ago. Having the molar quantities greatly helps in checking the yield data, something I always do as a reviewer when solvates are claimed.

It is often the case that yields are incorrectly reported for solvates, and I made this mistake myself once (“Regiospecific and Stereospecific Reactions of Ph3C+ PF6– with Rhenium Alkyls (η-C5H5)Re(NO)(PPh3)(R); α vs ß Hydride Abstraction”, Kiel, W. A.; Lin, G.-Y.; Bodner, G. S.; Gladysz, J. A. J. Am. Chem. Soc. 1983, 105, 4958-4972. DOI: 10.1021/ja00353a020). Hence, ever since the mid-80s I have had a group handout on this topic with the example from the paper. The present version is on my research group website and pasted below:

Solvates: Avoiding Common Errors

I’ve never sent this out for external review, but this post is a step in that direction. Subject to input, it may eventually become an appendix in the author guidelines of Organometallics.

One point is that a solvated compound has a greater FORMULA weight than an unsolvated compound. This is the quantity that must be used in the yield calculation. The yield associated with a solvated product will always (for a given mass) be lower than that associated with an unsolvated product.

Another point is that the presence of solvate molecules must be independently verified, with NMR being the obvious choice, but there are other options. I’ll refer readers to the handout for this. I’ll also comment that hydrates are the most difficult types of solvates to treat quantitatively, sometimes there is no perfect slam-dunk solution for them.

Thus, with respect to the Dorta manuscript and Drinkel thesis, we will be focusing (apart from many other questions) on whether the reported procedures give solvated or unsolvated products (it cannot be both), and then whether the yields given are correct (we have done the calculations both ways, and also looked at the NMR spectra per the group handout).

Update 6 (8/16): Emma’s mother speaks up at Synthetic Remarks: In defense of Emma

Dear Dr Kieseritzky

I hope you don’t mind me contacting you, but I would just like to thank you for your comment on ChemBark. My name is Mary-Anne Drinkel, and I am mother of Emma. We are very proud of our daughter she has worked hard and conscientiously to earn her first class degree at Durham, her PhD at Zurich, and presently her Post doctorate work in Brazil- we know that fabricating data would be alien to her. I cannot believe that her good reputation, built up over these years can be destroyed in a week. I know nothing of the academic community, but the hostile and aggressive comments left on the blog sites are unbelievable. I don’t know if Reto Dorta was careless or has done a very bad thing, but I do know that Emma is the innocent party in this affair. How many PhD thesis could withstand the hostile scrutiny that Emma’s has been subjected to, with these bloggers determined to find evidence of wrongdoing – boasting about who broke the news first.

Emma’s husband has a new industry position in Switzerland, and they will be moving back to Europe very soon; this means Emma will be applying for jobs – she fears this affair will affect her chances, as she would be honest with prospective employers about her situation. They had decided to leave the academic world long before this episode because the competitiveness and political environment of university life was not for them. Emma is devastated that her good name at Durham and Zurich University will be forever tarnished by this affair.

My husband and I have felt so sad and so helpless as these events have developed – when I saw your comment that was sympathetic to Emma’s plight, it was the first bit of humanity I had witnessed in the whole affair, and I am grateful to you for that. Emma will get through this, she is resilient and has the support of her husband, family and friends – but we feel so angry that Emma has been subjected to this through no fault of her own.

Once again thank- you,

Best wishes,

Mary-Anne Drinkel

Mitch

18 comments

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  1. chickenwowshi

    Well… couple things…

    1) I felt the pressure that this student can be under…
    2) The PI is kinda screw by promoting scientific fraud
    3) All the authors should really proof-read well and make sure every little detail gets fixed before submit
    4) Even though it’s a SI, the reviews should still do their job better rather than just quickly read through the main manuscript.
    5) There might be some “favors” going on… it could just happen to be reviewed by their good friends :)
    6) Might need to read higher impact journals…

    kinda want to see how things go… how things get resolved…

  2. Paul Kovac

    Judging by discussions with colleagues in organic chemistry, we have a crisis in executing and publishing synthetic chemistry (inflated yields, unassigned NMR spectra, no optical rotations for chiral compounds, m.p.s for amorphous solids or for residues after evaporation of solvents, HRMS in lieu of combustion analysis as proof of purity, solvation adjustment of calculated figures for amorphous compounds to fit results of combustion analysis, and similar nonsense has become virtually norm, also in so called high impact journals). If you want reliable results, you have to look for them in journals published before the seventies of the last century. Part of the problem we face is caused by lack of qualified referees and too many unnecessary new journals whose pages have to be filled. Trust in published work can only be restored when the field starts policing itself.
    Please read also: Chemistry and Biodiversity 2004, 1, 606-608.

    1. Ari Koskinen

      Paul makes a point in saying that we should start looking after our own more carefully. I often wonder, how come we have become so shy in defending scientific integrity that we accept inadequate and poor experimental work, shabby reporting, salesmanship instead of honesty in papers, let alone outright lies. This particular case is an extreme case of fraud, the supervisor ASKING the student to MAKE UP elemental analysis data!!! There simply is no excuse to such behavior.
      Poor refereeing should not be accepted from any journal, let alone ones that boast a high reputation. The journals should look after their reputation and make sure that the referees understand their responsibilities, not just keeping the rejection rates high. I have heard from too many distinguished professors in their field that they have given the manuscripts assigned to them for refereeing to their younger colleagues (post docs or even PhD students), and then just forwarded the younger persons statement as such. If they had even discussed the refereeing process and criteria, that could have been educational but such avoidance of duties is not good for science. But, how can I trust a journal that accepts such poor refereeing? I don’t.

      1. Zostra

        I asked several Germans of differing abilities in English (N = 3) about the language question. They all opined that this would not be a normal (i.e. innocent) mistake. “Just make” could indeed be an understandable German mistake if “just do” was intended, but “just make *up*” wouldn’t be at all.

    2. Dave

      Paul Kovac,

      I am quite puzzled by your indictment of HRMS being reported in lieu of elemental analysis in synthetic organic chemistry. The typical SOP for the characterization of an organic compound and its purity must be the following: 1H NMR, 13C NMR, HPLC or GC analysis, IR, melting point (if solid), specific rotation (if chiral), and either HRMS or EA. Unless you truly believe there is some inorganic, NMR silent impurity that could be produced in the synthesis of a compound, what you are asserting in this statement sounds quite unreasonable. Furthermore, to say that you have to go to articles pre-1970 to get reliable data is simply not true. I do completely agree with you, however, that inflated yields and unassigned NMR spectra are completely unacceptable.

    3. Vic

      Although I agree with the most of your statements in your comment as well as your commentary in Chemistry & Biodiversity, I think that you are also missing two important points. As a referee for many of the “low-impact” journals, I am constantly straggling with the following problem. In many manuscripts, especially from certain specific countries (no offense – just experience), authors provide almost perfect elemental analyses for their compounds. Quite often, however, such analyses are done “on-site” (at the same academic institution) and do not correlate well with the spectroscopic or redox properties of the target compounds presented in manuscript. Several times, I got angry replies from the authors (during resubmission of revised manuscript) that their compounds are pure because elemental analysis is perfect! Another problem a lot of inorganic and organometallic researchers are familiar with is that quite often, transition-metal and lanthanide compounds tend to form metal oxides, nitrides, and carbides at combustion analysis conditions, which can cause deviation from an “acceptable” agreement between theory and experiment. What one should do in this case if all other data (say 1H, 13C NMR, HRMS, X-ray crystallography, UV-vis and CD spectra) clearly support the purity of compound?

  3. M. Ogliaruso

    You should remove the reviewer from you list for not calling that statement to the attention of the editor. Did the reviewer actually read the submission? Poor, very poor reviewing.

    1. Yor Aretard

      If you’d been paying any attention you’d have read long ago that the reviewers never saw the version of the SI with the statement in it.

  4. Paul

    It may not be the easiest thing to implement (at the very least, it is outside of my skill set), but perhaps a system should be implemented where by any listed author should be sent an email upon manuscript submission, and then the manuscript only forwarded for the consideration of the editor when all listed authors have acknowledged the content of the manuscript. This way it would place more onus on all article contributors to ensure that all work submitted is of the quality that they want. At that point in time, all authors independently assume full responsibility for the work in question, in a similar fashion as an engineer stamping a technical document.

    1. Caligari

      not only that it is possible, but it is normal for submissions in computer science (i.e., every serious submission management system does it by default)

  5. Justin Peukon

    Thus, compound 14 (in the SI) is an “intermediate” isolated with 93% yield !

  6. Patrick

    I am condemning the alleged actions of this PI, but has anyone considered that this non-native English speaking PI simply phrased his request poorly (remove ‘up’ and the sentence in question completely changes its meaning) ?

    1. Rico

      It would be fascinating how you would perform an EA when there is the whole atlantic between you and your compound. She is already long gone to brazil and has done her work.

      The comment of her supervisor is not only outrageous but also stupid. If there is no EA, reproduce the god damn procedure (that’s what they are made for in the first place) and perform an EA. And of course, update the procedure in the SI with the new experiment. If you want to publish, do it together with the PhD, not years after he or she has finished. It’s always the same, the number of publications is getting more important than the science itself. How many papers are published and only read once? How many “scientists” wander around competing between 98 and 99,99% ee ? Who the fuck cares? A yes and I almost forgot… just take whatever synthesis you find in a book, do it without solvent, and if it works just okay… you have another paper. And don’t you care about 9 of 10 experiments exploding into students faces, you still have this one paper more this year!

  7. Christopher

    Yes, many German native speakers are not familiar with the phrase “make sth. up”

    1. German Speaker!

      so those German speakers that you’re talking about should first work on their English before taking a position at an English speaking university!

  8. reviewer

    PhD student should be the last person to blame (if the investigation shows some wrong doing). I am wondering why the Uni Zurich and Uni West. Australia do not issue any statement to show that they are in fact sensitive and looking the matter closely! After all the guy who apparently forced the student is a professor at UWA and perhaps reviewing many grant applications and/or swallowing other people opportunity in competitive funding by “making things up” as papers and wasting x millions worth of equipment and technical staff time for just “making up things”. That would be nice to see the universities are actually care about who is working for them as a “researcher”.

  9. m

    For the record, an editorial review of this case has been published.
    http://pubs.acs.org/doi/abs/10.1021/om401186q

  10. Thomas Hiltebrand

    What is that all about? Anyone which does make chemical research knows. that e.g. metal-complexes often fail to have 100% correct results. That is due to formation of e.g substances like FeC3 with a mp of about 1800 C during burning. I am Not aware, that anyone in academics does median with 3 sigma errors for elem. analysis. Usually, then the poor student has to make e.a. till the result fits. Hopefully he has a clean oil diffusion high vaccum pump in good shape and a stable substance, which desn’t decompose durung drying.
    In the case of some rhenium-complexes, a Professor even tried to refuse me, to let the crystalls x-rayed because the elem. analysis seemed to him not okay. Okay they contained THF, so the “false” result was in the end pretty much okay. The values of the X-Ray where that good, that you couln’t even hide one electron. The results weren’t published, for years, although I had to sign that they were public because that time, Diploma Work was by law public property. Most probably, that was the problem, so it couln’ t be patented…

    There were rumors that somebody blackmailed my professor, and took a long time untill some others came up, claiming they had synthesied them… After 7 years. Just that time, the docs woul be thrown to the trash…Just in that time, where in my renting house some persons came out of the appartment door of my neighbors, when they came home, but no fingerprints were taken by police…sheets where missing in my appartment etc. When my car was broken in, the police instead hurring for hunting the thieves, which I saw, and inmediatelly called the police, I was taken to interrogation room…

    The police never really investigated, it even came worse, I had to hear, that apparently my voting ballot for the election of the regional judges was checked. ” Er hat alle Staatsanwälte aussortiert…” Translated: He has removed all the states prosecutors. Sorry too much for even the most patient person. When I went to police,for sueing these, tow policemen told me, that they weren’t responsible, and that I should talk to some others, the second claiming that I would be mentally ill. Years later, some girl in Asia told me, she heard about, it was claimed that I couln’t speak english, and therefore the publication was never made. Gosh…

    Facts is, that apparently the in the case of Dorta the student did the work herself, so she didn’ get it from somebody else, —whereas some others seem to need that—, and that most probably she had the usuall troubles with elem. analysis may be because the intermediate was not stable enough and therefore: So what? Wo gehobelt, wird da fallen Späne. Only those who work can make mistakes… All the other keep their shirt (too) clean.

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