How large molecules cross narrow pore entrances

How can a snake swallow a mouse bigger than its mouth?

Weird as it seems, questions like this emerge very often at the molecular scale. For example, we can fill porous materials with molecules larger than the diameter of the pores: in this way, we may obtain devices for energy and health applications. What makes this useful process possible? Flexibility is the key: both the porous host (the “snake”) and the molecule (the “mouse”) must deform for the process to occur. But here, contrary to the mouse-snake case, cooperation between the two partners is needed.

We captured the passage of a bulky molecule through the very narrow opening of one of these pores. We did this by computer simulations, because it is very hard to get such information experimentally. To get an idea of what we found, you don’t even need to read the paper – and i’m not kidding. Just look at the movie below!

What we’ve seen first, is that the pore is slightly larger at its entrance. This surely helps the molecule to go in.

Second: contrary to the mouse, which would escape the snake as fast as it could, the molecule is indeed “magically” drawn to the pore entrance – by electrostatic forces.

“So what?” – you may say.

Keep in mind that the molecule is still larger than the pore opening. No kind of “fatal attraction” could do the trick, in a world of rigid bodies.

We’ve found that the molecule can pass through the opening and slip inside the pore only because it’s flexible, and its motion is “in tune” with the vibrations of the porous matrix. All this factors cope to make the entrance process more favorable than the exit process – that’s why the molecule gets finally swallowed by the pore, and remains trapped inside the material.

For me, it was very nice to see how bulky molecules manage to pass through narrow openings and travel inside a porous material. But finding out the reason why they stay inside was, probably, even more exciting:  because it explains how materials of this kind can form and remain stable. Which is exactly one of the things you may need, in the quest of  easier and smarter ways to produce better materials.

newchannel
Acknowledgments
 As we have to give credit where credit is due, i must confess that i borrowed the mouse-and-snake idea used in this post. But you’ll never know from whom. Me neither: (s)he was an anonymous referee of the paper. I am very grateful to this person: i can hardly imagine a nicest way to sketch our work.
Update: 
Many thanks, of course, also to ChemComm for the cover!
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4 thoughts on “How large molecules cross narrow pore entrances

  1. Wonderful work.. i m really very excited and interested. I have a question for you. kindly clarify. generally encapsulation is carried out using ion exchange methodology. during encapsulation, the metal ions will be leached out , in order to maintain the charge neutrality. what happen in your case.
    thank you

    Liked by 1 person

    1. Hi Chandra, thank you very much indeed for your nice words, your interest and for leaving some comments here! Concerning your question, in our case there’s no leaching of metal ions (K+) from the zeolite because the adopted PDI dye is neutral. Therefore, you don’t need to use ionic exchange to encapsulate this dye inside the zeolite. Dyes of this type are generally inserted at high temperature conditions, approx. 260 C. The insertion procedure is described in more detail in this reference: 10.1002/chem.201504404. Hope this helps!

      Like

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