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Let us assume that my opponent is playing a Shaddoll deck, and has activated "Shaddoll Fusion" on the first turn of the game. Since I have not taken a turn and have no monsters special summoned from the extra deck on my side of the field, the opponent is unable to send the Fusion materials from deck (part of "Shaddoll Fusion"'s effect), but can still Fusion summon using materials from hand.

Even though they can't use the part of the effect that sends monsters from deck to graveyard, and I still able to chain "Ash Blossom & Joyous Spring" to negate the effect of "Shaddoll Fusion"?

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You will be able to chain Ash Blossom to the activation of Shaddoll Fusion.

Ash Blossom reads:

When a card or effect is activated that includes any of these effects (Quick Effect): You can discard this card; negate that effect.

Because Shaddoll Fusion includes the effect to send cards to the graveyard it counts towards being Ash'd. It doesn't matter if you actually have a special summoned monster on your field, simply having that effect in its effect text makes it viable.

Source: https://www.db.yugioh-card.com/yugiohdb/faq_search.action?ope=5&fid=20586&request_locale=ja

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