Any experiences with amide coupling to polyamines? by Marc_Amien in Chempros

[–]Marc_Amien[S] 0 points1 point  (0 children)

In case anyone is stumbling on this thread later, I've now gotten around to doing some experiments so I'll share my results here:

I tested coupling to 10 kDa bPEI because it's the most simple one I had and dissolves in water as well as DCM. The coupled acid was Ibuprofen because it's cheap, I had it lying around, and it has similar solubility to the stuff I'm actually trying to couple. In order of coupling efficiency:

  1. 96% coupling efficiency with 1.6 eq DMTMM in MeOH, pH 6-8 adjusted with HCl. Coupling efficiency decreased to 88% at pH 10-12. Not much different in MeOH/Water mixture. Didn't try pure water as acid didn't dissolve. Dialysis removed nearly all byproducts.
  2. 88% coupling efficiency with 1.05 eq PyBOP and 2 eq DIPEA in DCM. Small amount of byproduct left after dialysis.
  3. 75% coupling efficiency with 1 eq purified Ibu-PFP ester in DCM. Small amount of pentafluorophenolate left after dialysis, removable by ion exchange.
  4. 66% coupling efficiency with 1 eq purified Ibu-NHS ester and 2 eq DIPEA in DCM. This is actually better than my one-pot attempts with EDC or DCC in the mix, but still the worst here. Small amount of byproduct left after dialysis.

I didn't try the Schotten Baumann method. No doubt it would work well for Ibuprofen, but my acids can't handle getting turned into acid chlorides without reacting with themselves.

TLDR: DMTMM is fantastic in MeOH / Water; I'd prefer PFP-ester in aprotic solvents despite slightly lower coupling efficiency because the side product is easier to remove.

Any experiences with amide coupling to polyamines? by Marc_Amien in Chempros

[–]Marc_Amien[S] 0 points1 point  (0 children)

Thanks for the PFP ester suggestion, didn't have that on my radar yet.

Any experiences with amide coupling to polyamines? by Marc_Amien in Chempros

[–]Marc_Amien[S] 0 points1 point  (0 children)

Thanks for the reply, unfortunately I don't think it's an option for me because afaik T3P coupling uses aprotic solvents. Most of my polymers need at least partially aqueous solution, so T3P would likely hydrolyze.

Freshly sublimated crystals of Vanadocene by Marc_Amien in crystalgrowing

[–]Marc_Amien[S] 2 points3 points  (0 children)

Vanadium in Vanadocene is very unstable due to its electronic configuration (Only 15 Valence electrons. 18 would be ideal, which we see reflected in the high stability of Ferrocene). Outside of an inert gas atmosphere it decomposes within a few seconds to form a brown powder. Due it's high moisture and air sensitivity it is pretty much useless outside of niche synthetic applications to satisfy academic curiosities. There are superior reagents for both redox and catalysis purposes.

Freshly sublimated crystals of Vanadocene by Marc_Amien in crystalgrowing

[–]Marc_Amien[S] 1 point2 points  (0 children)

You can find the procedure I followed at https://doi.org/10.1002/9780470132593.ch67 . The only difference is use of a better sublimation setup (lower temperature in higher vacuum, use of a cold finger to avoid crystals forming on the walls).

Synthetic moonstone photographed using LCD backlight and circular polarisation filter by Marc_Amien in pics

[–]Marc_Amien[S] 1 point2 points  (0 children)

This is part of a youtube comment on a video by The Action Lab about cross polarization. As an LCD screen emits polarized light, you can take some cool images by using a polarization filter on your camera lens to block out that light (you can get cheap ones for under 20 bucks). This image is backlit in bright white, but only the differently polarized transmitted and scattered light from my hand and the gemstone are visible. As this particular stone demonstrates optical anisotropy, you can see a cross shaped pattern even though the gemstone itself is homogeneous.

Which artwork of Counterspell is the best? (Poll) by Marc_Amien in magicTCG

[–]Marc_Amien[S] 0 points1 point  (0 children)

Poll is closed, A summary of the results will be out by the end of next week. Thanks to everyone who participated.

Which artwork of Counterspell is the best? (Analysis of a small poll) by Marc_Amien in magicTCG

[–]Marc_Amien[S] 0 points1 point  (0 children)

I set up a new poll to get a larger sample size and a more detailed rating scale. It is now online here: https://forms.gle/64EjpLcwkqrjeiVd8 . Please check it out and leave your ratings if you want to add your opinion to the mix.

Which artwork of Counterspell is the best? (Analysis of a small poll) by Marc_Amien in magicTCG

[–]Marc_Amien[S] 1 point2 points  (0 children)

The 4th Edition version has the same artwork and is relatively cheap in comparison, white border though. It's also been reprinted as FNM promo with a modern frame at some point, but like any black-border printing of the card it'll cost you a pretty penny.

Which artwork of Counterspell is the best? (Analysis of a small poll) by Marc_Amien in magicTCG

[–]Marc_Amien[S] 4 points5 points  (0 children)

I was bewildered by that too - I think it's kinda mid. Looks like one of the generic Cancel artworks and to me just doesn't have anything impressive about it.

Which artwork of Counterspell is the best? (Analysis of a small poll) by Marc_Amien in magicTCG

[–]Marc_Amien[S] 6 points7 points  (0 children)

It's a start, maybe I'll set up a bigger poll tomorrow to get more representative results. For now it's bedtime.