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They are ideal for it, since they have resistance.
There is a subset of Custodes who take missions across the galaxy but nobody really knows what they are doing and why.
the reason sisters of silence are anti psyker specialist is their blank gene
culexus assassins also have that gene and they have equipment that weaponize it so they are extremely specialized to kill psykers
As far as I know, they supported:
- The Death Guard during the Xenocide of the Jorgall (Flight of the Eisenstein)
- The Space Wolves against the Thousand Sons during the Razing of Prospero (A thousand Sons/ Prospero Burns)
The are basically described as soulless with a black hole where their soul should be sucking warp manifestation even tugging on the souls and psyche of normal mortals.
To a normal human they cause extreme unease your skin crawls, you feel doom wash over you, maybe even sick to your stomach this is why most blanks even ignoring their rarity are often killed by their own families.
To a Psyker they are agony incarnate the loss of their connection to the warp causes pain both mental and physical if not lost of consciousness the stronger the Psyker the worse it is.
To a Daemon they are like death and a one way trip back to the warp as they suck out all the energy binding them to the material realm, once again other then the strongest beings it's a forgone conclusion.
Add to this Sisters of Silence are trained to be able to control and focus their aura to the point that even non Psyker Space Marines can be thrown off balance letting them go toe to toe with even the emperor's angels as otherwise normal people.
Then you add they can operate in teams sisters don't "help" against Chaos Psykers they hunt them.
Sisters of Silence and Custodes are best known for guarding the Emperor in his throne room but they do other stuff too.
In the case of the Sisters of Silence, they are directly involved with the Great Tithe, at least where psykers are involved. The psykers they gather up are then either sorted into various parts of the Imperium, or sent off to be the Emperor's psychic juice box. They are sometimes used to hunt down and kill rogue psykers as well. And plenty are stationed on the Black Ships.
They've formed various orders and offshoots all over the place also. Some are messing with the Webway, some are also permitted to pursue their own agendas so long as it means enemies die. Some take part in wars directly.
So while they are best known for guarding the Emperor with the Custodes, they do lots of other stuff as well.
There's way less Chambers than Chapters though.
I don't know if it is the duty of a specific Chamber or something else, but I have also heard sometimes Custodes will go protect some random dude because it was foreseen that he'd become important some day. So you could theoretically see a Custode guarding some nobody on some crap planet.
That part was shown in "A thousand Sons", where a single Sister held her own against Phosis T´Kar, Captain of the 2nd Fellowship.
He was also the Magister Templi of the Raptora Cult, which means he´s one of the strongest Librarians of his Legion. He only won because he deliberatly tanked the Sisters Blade just to get close enough to kill her.