Not yet.
“No direct or categorical and stringent proof of the dogma can be brought forward from Scripture. But the first scriptural passage which contains the promise of the redemption, mentions also the Mother of the Redeemer. The sentence against the first parents was accompanied by the Earliest Gospel (Proto-evangelium), which put enmity between the serpent and the woman: “and I will put enmity between thee and the woman and her seed; she (he) shall crush thy head and thou shalt lie in wait for her (his) heel” (Gen., iii, 15). The translation “she” of the Vulgate is interpretative; it originated after the fourth century (”Katholik”, 1893, 425), and cannot be defended critically. The conqueror from the seed of the woman, who should crush the serpent’s head, is Christ; the woman at enmity with the serpent is Mary (Hoberg, “Genes.”, p. 50; cf. Leimbach, “Messianische Weissagungen”, 1909, pp. 5 sq.). God puts enmity between her and Satan in the same manner and measure, as there is enmity between Christ and the seed of the serpent. Mary was ever to be in that exalted state of soul which the serpent had destroyed in man, i.e. in sanctifying grace. Only the continuous union of Mary with God by grace explains sufficiently the enmity between her and Satan. The Proto-evangelium, therefore, in the original text contains a direct promise of the Redeemer, and in conjunction therewith the manifestation of the masterpiece of His Redemption, the perfect preservation of His virginal Mother from original sin. The salutation of the angel Gabriel—chaire kecharitomene, Hail, full of grace (Luke, i, 28; cf. Bardenhewer, “Maria Verkundigung”, 95 sq.)—indicates a unique abundance of grace, a supernatural, godlike state of soul, which finds its explanation only in the Immaculate Conception of Mary. But the term kecharitomene (full of grace) serves only as an illustration, not as a proof of the dogma. From the texts Prov., viii, and Ecclus., xxiv, which exalt the Wisdom of God and which in the liturgy are applied to Mary, the most beautiful work of God’s Wisdom, or from the Canticle of Canticles (iv, 7, “Thou art all fair, O my love, and there is not a spot in thee”), no theological conclusion can be drawn. These passages, applied to the Mother of God, may be readily understood by those who know the privilege of Mary, but do not avail to prove the doctrine dogmatically, and are therefore omitted from the Constitution “Ineffabilis Deus”. For the theologian it is a matter of conscience not to take an extreme position by applying to a creature texts which might imply the prerogatives of God.”
Source: http://www.catholic.com/encyclopedia/immaculate-conception
For anyone who was wondering about “Mary crushing the serpent’s head” and where that comes from.