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After graduating from college, Bryullov travelled to Western Europe with his brother Aleksandr. While there, he became an accomplished historical painter. His best-known work, The Last Day of Pompeii (1830), was compared to those by Rubens and Van Dyck. The piece sparked a sensation in Italy, and established Bryullov as one of the finest European painters of his time. After the emperor gave him the high post in the Imperial Academy of Arts, Bryullov returned to his native Russia.

The painting "Last Day of Pompeii" is one of Bryullov's best-known works. It represents the destruction of an ancient Roman town by God. The artist spent six years on the picture, making many sketches and changing the composition several times. When it was finished, Bryullov showed it to the public in 1833. A real explosion of delight erupted, and it immediately won the Gold Medal. In 1834, the work was exhibited in Paris and Milan. It earned Bryullov the honor of being named an honorary member of several art academies and a gold medal.

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