Material-S is a Material, part of the system Unbreakable Dark materialized as a clone of Nanoha Takamachi during the Dark Fragment Incident. Her name is first introduced in The Battle of Aces in English Material-S and in Japanese "Exterminator of Starlight" without specific ruby-kanas. The "S" in her name is believed to stand for "Stars" or "Starlight", which are both associated with Nanoha. In The Gears of Destiny, it is revealed her rubied name is Stern the Destructor, which may be shortened as Stern. Stern is German for "Star." Her device is Luciferion. (Source: Nanoha Wikia)
Shooting Star Rockman, or simply Rockman, is the main character for the Ryuusei no Rockman anime series, manga and videogames. He is the Denpa Henkan (fusion) of Subaru with War-Rock, this gives him the ability to see and walk on Wave Roads and to use Battle Cards to fight viruses and enemies.
Shishigami is the ancient spirit of the forest. During the day, Shishigami resembles a great stag with many antlers, bird-like feet, and the face of a baboon. At sunset, Shishigami becomes Daidarabocchi, a huge god in a humanoid form that appears to be made out of stars with a long pointed face and tentacle-like spikes on the back. Shishigami is protected by the Wolf Clan. As he walks, flowers bloom up at his feet though they quickly wither and die. He is capable of both giving life and taking life away.
Middleman is a demon who dresses up as a gentleman: complete with a suit, top-hat and monocle. He seeks out people who no longer see a value in their own life and offers them a deal, their life a year from that day for a large sum of money. To seal the deal he has the person drink a potion called the "Banrikou", which this potion also marinates the organ in question to be devoured by the one who paid for it after the year. This potion gives off an aroma which lures other demons. He also appears to be a bit of a flank, as Kanna commented that he always forgets to inform the customers what they are getting into.
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