Retraction Watch

Tracking retractions as a window into the scientific process

Crystal confusion leads to retractions for optics researchers

with 23 comments

spectrochimica acta part aA mistaken molecular structure has led to a retraction and a withdrawal for group in India studying optical crystals.

Here’s the notice for “Crystal growth and spectroscopic characterization of Aloevera amino acid added lithium sulfate monohydrate: A non-linear optical crystal” in Spectrochimica Acta Part A:

This article has been retracted at the request of authors.

According to the author we have reported Aloevera Amino Acid added Lithium sulphate monohydrate [AALSMH] crystal is a new nonlinear optical crystal. From the recorded high performance liquid chromatography spectrum, by matching the retention times with the known compounds, the amino acids present in our extract are identified as homocystine, isoleucine, serine, leucine and tyrosine. From the thin layer chromatography and colorimetric estimation techniques, presence of isoleucine was identified and it was also confirmed by NMR spectrum. From the above studies, we came to conclude that AALSMH is new nonlinear optical crystal. After further investigation, lattice parameter values of AALSMH are coinciding with lithium sulphate. Therefore we have decided to withdraw our paper. Sorry for the inconvenience and time spent.

A comment on the March 2014 article was published in July. Here’s the abstract:

The title paper (Manimekalai et al., 2014) reports a slow evaporation solution growth of a so called ‘Aloevera amino acid added lithium sulfate monohydrate’ (AALSMH) crystal. In this communication, many points of criticism, concerning the crystal growth, NMR spectrum and X-ray powder pattern of this so called AALSMH nonlinear optical crystal are highlighted.

Another paper by the group, “Investigations on growth, phytochemical and optical analyses of Aloe Barbadensis’s amino acid added potassium dihydrogen phosphatenonlinear optical crystals,” is listed as “withdrawn at the request of the author” from Optik as of December 2013. We’ve written about Elsevier’s withdrawal policy before – a paper published ahead of print can be disappeared from the internet, without an explanation.

Here’s that policy, as stated on the withdrawal notice:

Withdrawn Articles in Press are proofs of articles which have been peer reviewed and initially accepted, but have since been withdrawn before being published in this publication. Reasons for withdrawal may be a decision by the author and/or editor, accidental duplication of an article elsewhere or because the content contravenes the Elsevier publishing policy in some way. Withdrawn Articles in Press are only visible to users when following an external link, e.g., a PubMed or DOI link. Such Withdrawn Articles in Press are not searchable or otherwise available in ScienceDirect.

We’ve reached out to the author and the editor, and will update with any new information.

Comments
  • Marco August 20, 2014 at 12:26 pm

    Srinivasan, who commented on this now-retracted paper, has earlier commented on several other papers, pointing out misidentification:
    http://www.sciencedirect.com/science/article/pii/S138614251301086X
    http://www.sciencedirect.com/science/article/pii/S1386142513008007
    http://www.sciencedirect.com/science/article/pii/S1386142513013796
    http://www.sciencedirect.com/science/article/pii/S1386142513009578
    http://www.sciencedirect.com/science/article/pii/S1386142513003508
    http://www.sciencedirect.com/science/article/pii/S1386142513007622

    Maybe an idea to contact him? He must have something to say after having pointed out mistaken identifications of new materials on seven occasions in SAA, and now finally have one group “do the right thing” and retract.

    Not that others haven’t noticed all those papers misidentifying supposedly new crystals in SAA
    http://www.sciencedirect.com/science/article/pii/S1386142513000358

  • Bill August 21, 2014 at 3:19 am

    Well-done to Srinivasan for taking the time to try to purge the literature of these incompetent misidentifications of known compounds, although I suspect this is just the tip of the iceberg. Meanwhile, the Editor(s) and referees of Spectrochimica Acta, which has a reputation as a decent journal, should hang their heads in shame for allowing such work to be published in the first place.

  • Bill September 18, 2014 at 6:26 am

    And here’s another one… http://www.sciencedomain.org/abstract.php?iid=638&id=33&aid=5953#.VBqywKNwaM8 based on more imaginary “doping”

  • Marco August 21, 2014 at 6:29 am

    Well, let me just say that these incorrectly identified compounds may not be the worst problem in SAA. They have published well over 100 papers (I can document this if needed) using fluorescence spectroscopy to analyze ligand binding to proteins which are either wrong (and often obviously so) in their methodology and interpretation, or where I have strong doubts about whether they did things right.

    For those with even the most basic knowledge of chemistry and proteins, they can have fun with this paper:
    http://www.sciencedirect.com/science/article/pii/S1386142511003805
    Note in particular their scheme 1. This is biochemistry 101: if the Trp residues are not located at the end of the chain, as is the case for BSA, there is no free carboxylic acid and thus the proposed reaction is impossible. However, even if the Trp *was* located at the C-terminus, the proposed reaction still is not plausible. And even if the reaction indeed occurs, how can you determine a *binding* constant for a covalent reaction?!

    Another example: if anyone here ever struggles making diaryl ethers, just ask the group that wrote this paper:
    http://www.sciencedirect.com/science/article/pii/S1386142511008390
    Apparently, it isn’t all that difficult (see scheme 2). They have at least two more papers where they propose a similar reaction with some kind of imidazole derivative

    Just out of curiosity, can anyone tell me how scheme 1 in that paper is supposed to work? Serious question. Either I miss some chemistry background, or that scheme has a mistake in it (too).

    And if anyone wants a great example of what the inner-filter effect can do with your fluorescence spectra, just check this paper:
    http://www.sciencedirect.com/science/article/pii/S138614251100816X
    Compare the fluorescence spectra in Figure 5 and the absorbance spectra shown in Figure 11.

    SAA is unfortunately far from alone in having published such flawed papers.

  • Srini August 22, 2014 at 2:39 pm

    You are correct. Several papers reporting growth of novel nonlinear optical crystals in Spectrochim Acta and also in many other journals are erroneous (See below for some more absurd claims which have been commented) .
    Regarding papers reporting growth of doped crystals it can be easily said that a majority of these papers should be trashed. The errors are obvious based on very simple chemistry. For example the claim of doping an amino acid like L-arginine into phosphoric acid, without even taking into account that the amino acid reacts with H3PO4. For details pl. see http://dx.doi.org/10.1016/j.jlumin.2013.12.035

    The main problem is many of these researchers (who are physicists) do not have the required chemistry background to understand the synthesis and more sadly they make the same errors during characterization.
    .
    http://dx.doi.org/10.1016/j.matlet.2014.05.174
    http://dx.doi.org/10.1016/j.ijleo.2014.04.054
    http://dx.doi.org/10.1016/j.ijleo.2014.01.075
    http://dx.doi.org/10.1016/j.ijleo.2013.12.082
    http://nopr.niscair.res.in/handle/123456789/25091
    http://dx.doi.org/10.1016/j.optmat.2013.03.029
    http://dx.doi.org/10.1016/j.solidstatesciences.2013.03.005

  • lhac August 21, 2014 at 10:00 am

    Scheme 1 of the second paper is an imidazole synthesis. If you take into account that they use NH4OAc as additional reagent (provides the missing nitrogen), it is entirely possible (they mention that reagent in the experimental part, but not in the scheme). In fact, they took the procedure from a 1970 paper: Chem Pharm Bull 1970, 18, 2000 (not cited here, but in one of their earlier papers), the authors of which cite an obscure paper: F. Lions and E. Ritchie, J. Proc. Roy. Soc. N. S. Wales,74, 365, 1941; but elsewhere the same type of reaction is called a “modified Debus–Radziszewski reaction” and traced further back to the 19th century (see in: DOI: 10.1002/cphc.201200343, ref. 27).

    Concerning the aryl ether synthesis, it is not impossible. It would proceed by an SNAr mechanism (compare to Sanger’s reagent), but I wonder why tyrosine OH should react faster than a free amine nucleophile.

  • DocMartytn August 24, 2014 at 11:57 am

    The Highlights section for the B12 paper includes:

    ‘Stern–Volmer plots showed upward curvy patterns'; much as I like the term ‘upward curvy patterns’ I am unsure if it is canonical.

  • Marco August 21, 2014 at 12:45 pm

    Thanks, I was missing a nitrogen indeed.

    I agree the diaryl ether is not impossible, but that isn’t the same as plausible :-)

  • JATdS August 21, 2014 at 2:14 pm

    Has anyone thought of stirring the hornet’s nest by contacting ALL SAA editors and drawing their attention to this blog post? Maybe someone could also provide a detailed list of PubPeer entries here, too. It appears, from the criticisms here, that there is a serious problem with the peer review and editorial oversight by the very same individuals who have been appinted to ensure the quality and accuracy of published papers that have allowed their journal to score an impact factor exceeding 2.1 (http://www.journals.elsevier.com/spectrochimica-acta-part-a-molecular-and-biomolecular-spectroscopy/). If the numbers claimed by Marco are right, surely that would require that the entire editor board be disbanded, at least, followed then by an independent panel to scrutinize the errors that Marco is pointing out. Whether we are talking about elephant femurs, aortas or chemical compounds, PPPR now must serve to not only correct the literature, but to also hold those who are placed in a position to ensure the quality control BEFORE a paper is published, i.e., the editors and “peers”, accountable for their failures and oversight. If indeed there are as many errors as Marco claims there are, then this is a unique opportunity for the scientific community to take charge and put pressure on Elsevier to scrap the current editor board and start afresh (because something fundamental about the analyses of papers is clearly flawed). I nominate Marco and Srinivasan to take this initiative forward.

  • Marco August 22, 2014 at 2:10 am

    I have already taken initiative 1.5 years ago. That ended with an Editorial
    http://www.sciencedirect.com/science/article/pii/S1386142512008530
    of which the content, I will be honest, was rather disappointing.

    I consider my communication with the Editors confidential, so I will not go into further details.

    Since that editorial, the rate of publications of these papers has reduced, those that get through mostly correct at least one of the prior common errors (failure to correct for the inner-filter effect), and I haven’t seen as many horrible errors as those I pointed out above. It isn’t 100% good, though.

    I have no intention to take this forward any further with SAA. It is not my direct research field (which makes it all the more ironic that I noticed the mistakes); SAA is not a journal I or anyone I work with ever uses; I and several colleagues have compiled a Special Issue for the Journal of Molecular Structure that discusses proper use of fluorescence to look at ligand binding (it is currently in press); and there are now some others within the directly-relevant community that are publishing papers pointing out the same issues and sometimes correcting older papers, so that’s it for me. The story would be different if I were nearing my pension, but for now my PhD students have earned the right I spend my precious time and efforts on educating them.

  • Yoso August 22, 2014 at 4:54 pm

    Interesting observations on the nature of research and publications As you stated the ones you cited that have no falsification or fraud – these are studies performed smaller institutions/departments with limited research infrastructure. Am not sure what the motivation or goal is behind these studies other than publications. Though not earth-shaking science, does this allow faculty/students to pursue some scientific research? Assuming it is done the right way.

  • KK August 22, 2014 at 6:46 pm

    fantastic observation – appreciate your time in analysing these papers. you are right – paper generating machines are being produced or have already been produced. it takes efforts like yours to uncover that the value of such research is not all that great. But at the positive side, it is a research paper for an undergraduate or a postgraduate student. As you said, it is a business model, when these students apply for graduate or postdoctoral studies, they have few papers to write in their cv. looks good on paper, right?

  • Srini August 24, 2014 at 2:06 am

    Dear Ihac – Your observations based on a detailed analysis of the recent papers reporting crystal growth in SA A and the conclusion thata large number of papers can be published (cargo-cult science) is very correct. But there is something more to the template on which the papers are modeled about which I am a bit more familiar with. Permit me to explain this.
    Normally a compound whose structure is reported already in Acta Crystallogr or some other journal is chosen for the crystal growth and related studies which are always reported in the same template.

    I will take an example from your list (last paper) namely the growth of L-Tryptophan p-nitrophenol (LTPN) crystal to appear in Jan 2015 issue of SA A.
    http://www.sciencedirect.com/science/article/pii/S1386142514010816

    The LTPN crystal reported in the above paper is already published in Acta Crystllgr. (Section E)
    http://journals.iucr.org/e/issues/2012/03/00/fk2052/fk2052bdy.html
    The name of the compound in the Acta E paper is L-Tryptophan 4-nitrophenol trisolvate. (Note that this is actually a 1:3 compound and so the name is correct).

    Notice the difference in the name of the compound in the SA A paper (L-Tryptophan p-nitrophenol) indicating this is a !:1 crystal and different.
    (In his abstract the author says that LTPN is novel non-linear optical crystal.) When one reads the SA A paper further it is noted that the unit cell of LTPN are in very good agreement with the reported values in the Acta Cryst (Section E) paper showing that the LTPN crystal is not novel.

    Changing names of known compounds and reporting them under different names (Most of these are just wrong) as novel crystals is a routine observation of the papers reporting crystal growth.
    Although this may sound unbelievable this does happen. There is one more paper on (L-Tryptophan p-nitrophenol) in Optik by another group also from the province of Tamil Nadu (see the link)
    http://www.sciencedirect.com/science/article/pii/S0030402614006147
    The code for the crystal in Optik is LTPNP and this author also claims that the unit cell of LTPNP is in agreement with the Acta Cryst paper. The OPTIK paper is also set in the same template that you have already identified.
    I am very sure that the SA A and the Optik papers are not the last ones but there will be many more papers on (L-Tryptophan p-nitrophenol) in OPEN ACCESS journals in the coming days because this is the normal trend that is observed for optical crystal studies.
    If one reads both the SA A and Optik papers (one will go mad) it will be noted that the details on the same compound are quite contradictory (Actually both papers are trash). The sad part of this story is that the reviewers of two different journals (SA A and Optik) approved publication of such nonsense.

    The story of another example in your list namely NLO activity of Diglycine Picrate
    http://www.sciencedirect.com/science/article/pii/S138614251401124X
    is more pathetic because this compound diglycine picrate (glycine glycinium picrate is the correct name) has been commented more times in the literature in the following papers.
    http://dx.doi.org/10.1016/j.saa.2009.12.045
    http://dx.doi.org/10.1063/1.3372622
    http://dx.doi.org/10.1016/j.saa.2010.09.009

    The last of the above (paper by Ghazaryan et al) clearly proves beyond doubt that glycine glycinium picrate is a centrosymmetric solid and hence cannot exhibit any SHG signals.

    Now in the new SA A paper, the authors do a theoretical study to explain the NLO activity of diglycine picrate when experimentally it has been shown that there is no SHG.

  • JATdS August 24, 2014 at 1:15 pm

    lhac, I have a particular interest in this case or set of case studies because several studies, as you point out, use plant material you list the rose petal case above). And my personal target is to fortify my claims that the plant science-related literature is corrupted. So, I am following this story very closely, even though, sadly, this is not my field of specialization. So, if you or others could explain, in more detail, the errors in plnat material-based studies, I am very willing to take my complain to the front line and take on the editor board head-on, without fear. One sense I had from your comment is that institutes might be targeting this jorunal precisely because of its now perceived weaknesses in detecting these problems with the papers. How then could such serious errors, or “bullshit science”, as you so eloquently put it, pass through the quality control net? Is there any remote possibility that a net of fae peer reviewers may have ben suggetsed through the online submission system [1], similar to what occured in the SAGE Publisher’s case at Journal of Vibrational Control [2]? It wouldn’t be too difficult to achieve this fraud, I believe, even with Elseviers EES system in place.
    [1] http://ees.elsevier.com/saa/default.asp?pg=mainpage.html
    [2] http://retractionwatch.com/2014/07/08/sage-publications-busts-peer-review-and-citation-ring-60-papers-retracted/
    The EES page for SAA states: “Criteria for publication in SAA are topicality, novelty, uniqueness, and outstanding quality. Manuscripts describing routine use or minor extensions or modifications of established and/or published methodologies (e.g. standard absorption, emission or scattering measurements; standard chemometry; FRET) are not appropriate for the journal. In addition, manuscripts describing analytical procedures that use established spectroscopic techniques, such as the quantitative determination of pharmaceutical compounds with optical techniques or the characterization of compounds with optical techniques in the course of a chemical or biochemical synthesis, will not be accepted for publication, even if they appear new or improved with respect to procedures previously used.”

  • JATdS August 24, 2014 at 12:57 pm

    Srini, you have shown quite a few examples of papers where you believe the paper’s cocnlusions are wrong and have given reasons why. Why, in your opinion, do you think that SAA – and possibly other journals – have not been able to detect these problems during the peer review? You refer to the weaknesses of the understanding of the authors (“The main problem is many of these researchers (who are physicists) do not have the required chemistry background to understand the synthesis and more sadly they make the same errors during characterization.”). but these are supposedly peer reviewed journals where peers and editors are supposedly experts. Are you suggesting the mass failure of peer review (and possible broad incompetence) on quite a massive scale of a medium level impact factor journal? And have you contacted the editor board (all members) with your queries, lists of claims and reasons? More than anyone else here on this page, you seem to have the insight – and thus the intellectual power – to cause radical change in this journal, by getting the editors and/or Elsevier to issue a whole set of errata and/or retractions and clean up the mess. May I suggest, if you have not already done so, making a PubPeer entry for each problematic paper and also, if you have the time and the patience, to start a petition in which you could contact 50 or 100 specialists who are not associated with the editor board and get them to back your claims. If you come forward to the editor board of SAA with a 50- or 100-complainer list, it will be extremely hard to avoid, or hide, the issue.

  • Marco August 24, 2014 at 1:01 pm

    If you like that one, how about this from the same journal
    http://www.sciencedirect.com/science/article/pii/S1386142512010074
    Interesting new species, no?

  • lhac August 24, 2014 at 7:16 pm

    @JATdS: I also wondered how such a large number of those template style articles could and still can make their way into that journal.
    I also assume that once you have number of authors publishing similar papers, they start to referee each others papers – simply because they work in the same field and get preferentially chosen as referees by the handling editor, there need not be any foul play.
    However, this only works if the assigned editor fails to see a problem with such articles in general… He/she could easily choose to send them to more critical referees, if he/she wanted to get them rejected. From some of the above contributions it seems that the editorial board should already be aware of the problems.

    Concerning the plant science aspect: I think the articles using rose leaves and the like should not be regarded as having connections to plant science. They simply use bio-materials which have a generally reducing character (because they contain carbohydrates or terpenes), which is enough to induce precipitation of elemental silver or palladium from their solutions. That is part of why those works are so pointless, because you could easily perform that same experiment on hundreds of other plant species samples or chemical reducing agents.

  • lhac August 24, 2014 at 7:46 pm

    Srini, thanks for the further info. I already guessed there must be a underlying copycat problem from the following strange observation: One of the articles used a test of crystal hardness and cited a strange literature reference:
    “Meyer E. (1951), ‘Some Aspects of the Hardness of Metals’, PhD Thesis, Draft.”

    I thought this was a strange reference, because why would you cite the “draft” version of a PhD thesis – from 1951? I mean, has the finalized version never appeared in the meantime?

    After a little googling (e.g., for the sentence “Some Aspects of the Hardness of Metals”), I found that the same reference had been used in many, many articles especially by Indian authors, sometimes writing (Name and initials and the strange word given as found in several articles):
    – Meyers, MA (Draft)
    – Meyers, MA (Dreft)
    – Meyer E (Dreft)
    – Meyers (Dreft)
    – Meyer (Dreft)

    As it turns out, the source is a PhD thesis from the university of DELFT by a certain Dr. “Mauritius Arnoldus du Toit Meyer”.

    Now, it is well known that the Dutch use far too many first names and I cannot entirely blame the Indians for not getting the name of that Meyer guy correct… – where do the first names stop, and where does the family name start?
    However, they all seem to copy the reference from some older papers, missing some letters in the process, or changing some other letters. Have they actually read that thesis?

    So, by googling for the above (false) reference, you will find a dozen of Indian crystallography papers, of which one must assume they copied from each other, or somewhere else… (starting on page 3 of google results, the first 2 refer to the actual thesis).

  • JATdS August 24, 2014 at 9:39 pm

    lhac, this is one classical case of “snub publishing”, a term I coined in 2013 to describe such cases (among others):
    http://www.globalsciencebooks.info/JournalsSup/images/2013/AAJPSB_7(SI1)/AAJPSB_7(SI1)35-37.pdf

  • Marco August 25, 2014 at 1:56 am

    Du Toit Meyer is actually South-African, and it is possible to get the whole thesis here
    http://repository.tudelft.nl/view/ir/uuid:f617b5af-e390-44ef-9e06-83028a38c2de/

  • JATdS August 24, 2014 at 9:52 pm

    lhac, thanks for that further insight. Indeed, your last part of the comment was of particular interest to me, and is in fact related to plant science, because the fact that literally tens of thousands of plant species contain similar or the same secondary metabolites (albeit at diffeent concentrations) suggests that we may be seeing the emergence of papers with the title similar to, using the study by Vimala et al. (http://www.sciencedirect.com/science/article/pii/S138614251400897X) as a random example (without any insinuations about the quality of their study):
    1) Optimization of reaction conditions to fabricate nano-silver using mungbean (Vigna radiata (L.) R. Wilczek) (leaf & fruit) and its enhanced larvicidal effect
    2) Optimization of reaction conditions to fabricate nano-silver using sunflower (Helianthus annuus L.) (leaf & fruit) and its enhanced larvicidal effect
    3) Optimization of reaction conditions to fabricate nano-silver using bitter gourd (Momordica charantia L.) (leaf & fruit) and its enhanced larvicidal effect
    4), 5), 6) etc. etc. with a different species for each paper, but using identical methodologies, and “paper template”.
    Do you see what I am saying? I guess this has more relevance (and concern) if we can know, clearly, how Indian scientists are rewarded for publishing. In this sense, perhaps Srini could be so kind as to indicate if there is a direct remuneration system, as occurs in China and Iran, for publishing in impact factor journals, so, for example, perhaps an Indian scientist (corresponding author?) might receive XYZ Indian Rupees X the IF score (just a hypothetical suggestion, but one that needs to be asked and explored).

  • Srini August 25, 2014 at 12:27 pm

    @JATDS: Something appears to be wrong with the review process in SA A and also Optik w.r.t. papers reporting crystal growth. In this context the following observation of Ihac appears to be very correct
    “I also assume that once you have number of authors publishing similar papers, they start to referee each others papers – simply because they work in the same field and get preferentially chosen as referees by the handling editor, there need not be any foul play.”
    Ihac has also made one more observation regarding the ciitations. This group of authors cite each other.Sometimes some of the citations (like the 1951 thesis) make no sense. It looks like even a majority of the citations are a part of the template. Sometimes when you look at the citations (for example an organic crystal sevreal papers on metal containing compounds which are totally unrelated are cited) a reviewer can easily make out something is wrong. But this has not happened.
    This only means the explanation of Ihac how erronoeus papers pass thro the peer review system. I have written to some (not all) of the Editors of SA A on this issue and so they are very well aware of this problem. The retraction of the ALoe Vera paper is itself a big story (Pl. send me an emaiil at srini@unigoa.ac.in and i will share with you some of this and may be your feedback can be helpful)
    i have also written to the Editor of Optik.(Prof. Theo Tschudi) and he is well aware of this matter. On two occasions he immediately responded and took action namely removal of the paper from the journal. In one of his responses he even said that he has to talk to the reviewers. But still I have no explanation as to why many erroneous papers still continue to appear in Optik

    Pl. note one thing. The journal of crystal growth is a more appropriate journal for reporting this type of work. But growth of crystals are reported in other journals (in fact in all types of journals) After the publication of a case study (http://www.sciencedirect.com/science/article/pii/S002202481000312X) which showed a large number of amino acid based crystals are erroneous, this journal probably shut its doors for dubious crystals (especially the ones based on amino acids) because the case study was authored by one of the Associate Editors and so he can easily detect adubious submission. So the papers were submitted to other journals especially SA A.

    I like to discuss with you on email about this to see what else can be done.

  • Srini August 25, 2014 at 12:53 pm

    @JATds; There is no monetary incentive for publishing papers in India. Of course, publication of papers is needed to get a promotion in the job from Asst. Prof to Associate Prof to full Prof. In India all teaching institutions (colleges and Universities) follow the Univ Grants Commission rules. According to this points (Academic Point Index) Just google the follwoing term
    UGC GUIDELINES FOR SCORING IN CATEGORY-III …
    and you will get the full details.

    The API s one reason why people want to publish.to increase their score. Only in good institutions or prestigious awards the selection committee takes into account the h index,,number of citations etc. the academic merit of the work etc. In the colleges and most Universities, they only look at the total number of publications which can probably explain more number of publications in Open access journals. I think some people do not mind to pay the publication cost (I don’t think most institutions have grants to pay publication costs) because the money invested in a Open access journal paper gives some points which can give the promotion.

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