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Is #OpenAccess a first world problem?


The goal of any scientist is to generate new knowledge and then it would be a fair assumption that most scientists are inclined to share that knowledge with as many people as possible in a noble effort to improve the world in which we live; in fact, that is the very -underlying- reason why we publish articles of all our research, so every bit of knowledge generated in our labs goes not only on record but is available for testing and questioning. The Open Access (OA) supporters rightfully wish that all publications were accessible to anyone interested without having a middleman such as a big publisher controlling access and making a profit along the way.

A while ago there was a rather noble initiative in Mexico to have all publicly funded research fully available to everybody; sounds reasonable but here is the catch: Our research would have to be published in a public online platform created, managed and operated by the state with public money. This means the Mexican tax payers would have to pay not only for research to be done but to be stored and curated also. On top of that, this platform would require to become somehow visible to other researchers in other countries in order for it not only to gather attention and recognition from the larger scientific community but also to get their proper scrutiny; and that might not a be task that the state is good at doing. Furthermore, once our research is made public through this platform we might have a copyright problem when submitting it to a mainstream traditional journal with a quantifiable IF and whether we like it or not – whether we believe in it or not – IF is a quick go-to measure with which researchers are qualified by current and future employers, in fact, permanence in certain institutions as well as organizations rely on the continuous publishing of peer reviewed indexed articles.

When I started doing research here at IQ-UNAM dollars were about eleven pesos each, they are now over twenty yet my budget is still pretty much the same and is always in pesos, not dollars, so a larger gap keeps building up. So to me, paying for an OA is becoming more and more expensive everyday and although there are very prestigious, legitimate, peer reviewed, indexed OA journals the publication fee is an important factor to consider. If I indeed have the money available I may better think twice about saving it by going to a traditional journal and use it for other purposes. And in the end, fair or not, does everybody really want to read about my calculations? I really doubt so. My personal take is to publish in a traditional journal* and then blog about it in a more relaxed way here, plus making it visible in several platforms such as Mendeley, Academia.edu or ResearchGate and share it with others whenever possible.

It would be fairly easy to assume from the title and previous line that I oppose Open Access publications but then again that would be a wrong assumption. The broader answer is that I am for OA but that I don’t think the current scientific landscape makes it a terrific idea. First, employers would have to stop fixating in IFs and prestigious titles and then there would have to be enough money for paying OA’s or making the decision between paying the fee or using the money for other things; and that right there is what makes it a First World problem to me.

New paper in PCCP: CCl3 reduced to CH3 through σ-holes #CompChem


I found it surprising that the trichloromethyl group could be chemically reduced into a methyl group quite rapidly in the presence of thiophenol, but once again a failed reaction in the lab gave us the opportunity to learn some nuances about the chemical reactivity of organic compounds. Even more surprising was the fact that this reduction occured through a mechanism in which chlorine atoms behave as electrophiles and not as nucleophiles.

We proposed the mechanism shown in figure 1 to be consistent with the 1H-NMR kinetic experiment (Figure 2) which shows the presence of the intermediary sulfides and leads to the observed phenyl-disulfide as the only isolable byproduct. The proposed mechanism invokes the presence of σ-holes on chlorine atoms to justify the attack of thiophenolate towards the chlorine atom leaving a carbanion behind during the first step. The NMR spectra were recorded at 195K which implies that the energy barriers had to be very low; the first step has a ~3kcal/mol energy barrier at this temperature.

 

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Figure 1 – Calculated mechanism BMK/6-31G(d,p) sigma holes are observed on Cl atoms

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1H NMR of the chemical reduction of the trichloromethyl group. Sulfide 4 is the only observed byproduct

To calculate these energy barriers we employed the BMK functional as implemented in Gaussian09. This functional came highly recommended to this purpose and I gotta say it delivered! The optimized geometries of all transition states and intermediaries were then taken to an MP2 single point upon which the maximum electrostatic potential on each atom (Vmax) was calculated with MultiWFN. In figure 3 we can observe the position and Vmax value of σ-holes on chlorine atoms as suggested by the mapping of electrostatic potential on the electron density of various compounds.

We later ran the same MP2 calculations on other CCl3 groups and found that the binding to an electron withdrawing group is necessary for a σ-hole to be present. (This fact was already present in the literature, of course, but reproducing it served us to validate our methodology.)

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Figure 3 – Sigma holes found on other CCl3 containing compounds

We are pleased to have this work published in PhysChemChemPhys. Thanks to Dr. Moisés Romero for letting us into his laboratory and to Guillermo Caballero for his hard work both in the lab and behind the computer; Guillermo is now bound to Cambridge to get his PhD, we wish him every success possible in his new job and hope to see him again in a few years, I’m sure he will make a good job at his new laboratory.

New Paper in JIPH – As(V)@calix[n]arenes


As part of an ongoing collaboration with the University of Arizona (UA) and the Center for Advanced Research and Studies (CINVESTAV – Saltillo), we are looking into the use of calix[n]arenes for bio-remediation agents capable to extract Arsenic (V) and (III) species from water. Water contamination by arsenic is a pressing issue in northern Mexico and the southern US, therefore any efforts aiming to their elimination has strong social and health repercussions.

As in previous studies, all calixarenes were optimized along with their corresponding guests within the cavity, namely H3AsO4, H2AsO4 and HAsO42- at the DFT level with the so-called Minnesota functionals by Truhlar and Cao, M06-2X/6-31G(d,p) level of theory. Interaction energies were calculated through the NBODel procedure. Calixarenes with R = SO3H and PO3H are the most promising leads. This study is now publishes in the Journal of Inclusion Phenomena and Macrocyclic Chemistry (DOI 10.1007/s10847-016-0617-0) as an online first article.

This article is also the first to be published by our undergraduate (and almost grad student in a month) Gustavo Mondragón who took this project on a side to his own research on photosynthesis.

Now my colleagues in Arizona and Saltillo, Prof. Reyes Sierra and Dr. Eddie López, respectively, will work on the experimental side of the project. Further calculations are being undertaken to extend this study to As(III) and to the use of other potential extracting materials such as metallic nanoparticles to which calixarenes could be covalently linked.

Quantifying σ-Holes – G09 and MultiWFN


Some atomic properties such as an atomic charge are isotropic, but every now and then some derivations of them become anisotropic, for example the plotting of the Molecular Electrostatic Potential (MEP) on the electron density surface can exhibit some anisotropic behavior; quantifying it can be a bit challenging.

It is well known that halogen atoms such as Chlorine can form so-called halogen-bonds of the type R-Cl-R in crystals with a near perfect 180° angle. This finding has lead to the discovery of σ-holes in halogens. σ-Holes are electrophilic portions of the anisotropic electrostatic potential in an otherwise nucleophilic atom. Recently, Guillermo “Memo” Caballero and I calculated the MEP for a series of trichloromethyl-containing compounds at the MP2/cc-pVQZ level of theory and the mapping shows evidence of such σ-holes as seen in Figure1. Those small blue portions on an otherwise red atom indicate that some electron density is missing in that position, which by the way is located at 180° away from the carbon atom.

But having the picture is not enough. We want to quantify just how strong are those σ-holes to effectively attract a nucleophile and perhaps perform some chemistry on the C-Cl bond. That’s when we resorted to MultiWFN, a Multifunctional Wavefunction Analyzer developed by Tian Lu (卢天) at the Beijing Kein Research Center for Natural Sciences. You can check the project leader list of publications here. Among many other capabilities, MultiWFN is able to print details about properties along a surface.

In order to work with MultiWFN you need to generate a *.wfn file, if you have a previous Gaussian calculation for which you want to analyze their surface you can run a guess=only calculation in order to extract the wavefunction from the checkpoint file. Here is a dummy of the input for such calculation

%chk=oldfile.chk
# output=wfn geom=check guess=(only,read) density=current
--blank--
Title Card
--blank--
0 1
--blank--
filename.wfn
--blank--

In our case, having a post-Hartree-Fock calculation, the use of density=current is mandatory to get the MP2 density matrix and not just the HF one. Running this calculation will generate the file filename.wfn which is now used with MultiWFN. When starting MultiWFN you get to see a terminal window like the one below in which you are asked to input the path of your wfn file:

1

After loading it you will get the following window with the various options available. Type 12// (these two slashes are mandatory) to get the quantitative analysis of molecular surface option.

2

Then you will be asked to define some elements of that surface (we used the default options 0)

3

The following screenshot shows the results section in which several maxima  and minima of electrostatic potential were found (7 and 11 in our case); a star is placed on the side of the global maximum. The value of the MEP at those points is given in Hartrees, eV and kcal/mol which I personally hate because there isn’t such a thing as a mole of ‘potentials’ (same argument as giving an orbital’s energy in kcal/mol, moles of what? orbitals? Personally, I don’t like it even if its valid).4

Their visualizer is activated through the option 0 and although it is far from pretty it is quite good enough to find the numbers corresponding to maxima and minima of the MEP on the isodensity surface. If we look for the maxima then we find for our example (CHCl3) that a maximum is located in front of each Cl atom in a straight line from the C atom. Now we get to put a number on the mapped isosurface provided by Gaussian or even import the file into Chimera.

5ccl3cn

We are still working our way around MultiWFN, I hope we can find the batch option, it would be most useful. In the mean time, Guillermo and I will continue to search for σ-holes in chlorinated reagents. Thanks to Guillermo for his ongoing work in this and other topics within the realm of organic reactivity.

Have you any suggestions or ideas to work with MultiWFN? Please share them!

Internal Symposium at CCIQS – 2016 edition


Having a symposium right after the winter holidays is a great way to get back in touch with colleagues and students; we get to hear how their work is progressing and more importantly I get forced to become focused once again after a few weeks of just not paying much attention to anything related to work.

This year our group has happily gained some additions and sadly seen some others leave in search of a better future. María Eugenia “Maru” Sandoval gave a talk on the work she did on Singlet Fission (SF) in the Fenna-Matthews-Olson (FMO) complex during a three month stay at the Basque Country University in Spain under the supervision of Dr. David Casanova. Aside her calculations regarding Förster theory and a modification to Marcus’ equation, Singlet Fission was explored by her as a possible mechanism in which the Photosynthetic complex FMO might transfer solar energy from the antennae to the reaction center; one that might explain the high efficiency of it.

SF is a fascinating phenomenon: So you get an excited state S1 for a molecule1 that has been struck with a suitable photon; this excited state can either radiate back to the ground state (S0) but if there were two degenerate and coupled triplets whose energies are similar to half the S1 energy then the excited state might decay into [TT]1, hence singlet fission. In some cases (e.g. polyacene crystals) one of these triplets might be located in an adjacent molecule, this creates a hole in a second molecule due to the same single photon! This means creating twice the current albeit at half the voltage in photovoltaic materials. Maru has explored the possibility of SF occurring in natural systems and we think we might be on to something; she will defend her masters thesis any day now and we should see a publication later on this year. After that, she is pondering a few interesting options for her PhD.

On the poster session, our lab was represented by Marycarmen Reséndiz, Gustavo Mondragón and Guillermo Caballero. Durbis Pazos just now joined our group so he didn’t have to present a poster but nevertheless showed up gladly to support his colleagues. Gustavo will work on other aspects regarding the photochemistry of the FMO complex while Marycarmen is working on calculating the electronic interactions of chemically modified nucleotides when incorporated into DNA strands. Guillermo had a poster on his calculations for another reaction mechanism that caught his eye while still working with the experimentalists. I’m pleased to say that Guillermo is close to being published and also close to leaving us in order to get a PhD in a prestigious university that shall remain unnamed.

Thank you guys for keeping up the good work and maintaining the quality of the research we do, here is to a year full of success both in and out of the lab! Any success this lab has is due to you.

New paper in JCC – drug delivery agents


Today, on the last day of 2015, we have received great news that our latest paper regarding thr study of calixarenes as drug delivery agents has been published in the Journal of computational chemistry (10.1002/jcc.24281)  

This work represents the continuation of our previous paper published last year in JCTC regarding the use of delivery agents for drugs used in the treatment of chronic myeloid leukemia; this time, two drugs were studied simultaneosly -sorafenib and bosutinib- increasing the chemical space by two. Once again the methodology for designing a suitable carrier employed a mixture of quantum mechanical calculations -in order to get that interaction energy between hosts and guests- and molecular dynamics simulations (1 microsecond) to assess the release of both drugs into thr aqueous media. 

I want to thank my co-authors for all the hard work invested in this publication: Mr. Luis Enrique Afuilar Who is currently getting a masters degree in the Netherlands, and Dr. Rodrigo Galindo from Utah University white whom a fruitful cooperation has evolved for good. 

I’d also like to take this opportunity to thank all the readers of this blog for their ongoing support throughout this year and to wish them all a successful and happy new year! 

XIV Mexican Reunion on Theoretical Physical Chemistry


Each year the Mexican community who works in the realm of computational and theoretical chemistry gathers to share the most recent work done around our country. This year, I tried to live Tweet the event and although I failed miserably in doing so -as well as in convincing others to join me- I’m trying to put together the things that caught my attention. I also tried to Storify it but I cannot embed the result here in WordPress.

María Eugenia “Maru” Sandoval just came back from a short stay in Spain where she worked with Prof. David Casanova on Singlet Fission theory applied to her work on photosynthesis. Here work was presented as a poster although we would have preferred she gave a talk.

  

Also, Guillermo “Memo” Caballero presented his recent developments in reaction mechanisms.   

Below there is a list of Tweets from the conference. If you are interested in any of these items please contact me for further information, or just, you know, google the people mentioned in each Tweet, it shouldn’t be too hard.

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Of course when you have a large meeting with so many people working with and on Density Functional Theory (DFT) you know that Perdew’s suggested ‘Jacob’s ladder’ of functional quality for chemical accuracy is bound to show up a few times.
I actually wrote a post that gravitates around this issue but using figurative painting as an analogue. You may find it here

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That is Pt “double bond” Sn. By no means I’m equating platinum to tin. No sir. Mulliken’s population analysis should not even been brought up anymore, should it?

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If there is water and ice on Mars then most definitely should be clathrates. (Please excuse the misspelling throughout, though.)

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The rest are the previous announcements which were aimed to generate the momentum for the live tweeting thing.

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“Not!”

I hope I can make this a thing next year during the 15th edition of RMFQT. I had the honor to be the first speaker and I will upload my presentation soon.

248th ACS meeting – San Francisco 2014


This is my first time giving a talk at the ACS meeting so I’m a tad nervous but also excited about the possibility to listen to so many great researchers and hopefully interact with some of them, although such a massive event is hardly the best place to build a network.
My talk will deal with our recently published work on calixarene based drug carriers and the new results we are currently getting, and will take place on Tuesday 12th at 16:15 at the session regarding the use of small macrocycles in drug discovery. Feedback is very important to us so we look forward to some heavy criticism of our results.
If you are there, download the free app which will show you around the different presentations and stands.

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I will also make use of twitter to move from one lecture to another. See you there!

Nice Energy Level Diagrams with rxnlvl


Once again our friend at Eutactic has provided us with a way to create nice energy level diagrams and was kind enough to let me reblog his post. If you haven’t checked his blog please do so and encourage him to write more often.
This post is best served with: https://joaquinbarroso.com/2012/06/13/1027/

eutactic

I have written a bit of code lately which automates the process of constructing chemical reaction energy level diagrams rather well. It’s called rxnlvl. It’s written in Python, outputs to SVG (Scalable Vector Graphics) and is GPL3. I’m not a ninja programmer by any stretch of the imagination, however the program is basically functional, and in my estimation yields quite attractive results.

ImageYou can check it out at https://github.com/eutactic/rxnlvl

Enjoy, and if you find it useful I encourage you to show me what you’ve done with it.

 

Regards,

    -r

View original post


All credit is due to Laura Keith McMaster! Also thanks to irreverentreview.com for allowing me to reblog this witty post.
Thanks to all readers who’ve been following my blog, I wish you all a very happy holiday season and may the following year be filled with interesting and publishable data!

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