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Valentine went to Paris in the 1840s to learn the daguerreotype process. In the early 1850s Valentine had opened a portrait studio in Dundee, Scotland, which specialized in cartes-de-visite. Valentine founded Scotland's second largest photographic establishment, Valentine & Sons, in Dundee. Johnson gives the date of establishment of the firm as 1880, with Valentine dying in the same year; Spear mentions that the firm existed in the 1870s. After Valentine's death, the firm was run by his sons W.D. and George D., and is still in existence today.