This question has been addressed “scientifically” a couple times before… Mind you, not sure how well these explanations stand up to scientific scrutiny, but I’ve heard this particular explanation about polymerization of phenolic compounds from multiple people. And it seems to make sense.
Most recently from Doug Hein here: https://www.wineberserkers.com/forum/viewtopic.php?p=3153685#p3153685
Regarding the shutdown, much of it has to do with chemistry. Many of the phenolic compounds in wine, like tannins, can and do polymerize. They also bind with other aromatic compounds that effect taste and aroma. The polymerization process is the start of the shutdown. These polymer chains continue to grow and link, binding up much of the flavor of the wine. At some point, they become to long to remain in suspension and start falling out as sediment. They also become unstable and weak and start breaking apart, releasing the other compounds that have been bound up. When this occurs, the wine starts opening up. It seems to happen fairly rapidly at both ends.
After the wine reawakens, then it’s really a matter of continuing evolution of the aging process and all of the slow reduction reactions ongoing in the bottle. The first phase is prominent primary fruit, integrated tannins and the lovely earthy nose of Bordeaux. Beyond that is the shift to more of the interest tertiary flavors and the gradual fading of primary fruit. Of course, all this and the timeframe is dependent on the structure of the wine. For example, that 2005 Leoville Barton that is drinking so well now, doesn’t have what it takes to be the wine at 35 years old that the 1982 Montrose was I recently had was. But it’s a wonderful Bordeaux to drink now and for another 10 years.
I think this makes a lot of sense but that we need to give more emphasis to the wine’s redox chemistry. Especially if we want to offer an account for why white wines shut down. To do this, we really need to factor in closure too, as different closures have different oxygen transmission profiles over time. But I think it’s clear that the higher a wine’s redox potential, i.e. the stronger its tendency to move in a reductive direction, the longer it will tend to shut down, all things being equal (which, thanks to closures, they seldom are!). So a low pH white with appreciable dry extract from the skins (flavenols and other antioxidants) will have a higher redox potential and tend to shut down harder and longer.
Redox…what an elusive thing. I used to work on the chemistry of the Earth’s deep interior, where redox can often be understood in terms of simple systems that are more or less fully describable. Even there, I was often left scratching my head, as were many people much smarter than I am. Fully understanding the redox state of a much more complex solution like wine, and how that evolves with time, really is a holy grail topic and one I hope we see much progress on in the next couple of decades.
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