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\documentclass[12pt]{article}
\pagestyle{empty}
\usepackage{datatool-base} 
\begin{document}
Purify early.\DTLsetup{initial-purify=early} 

\'{a}bc (accent command): \DTLGetInitialLetter{\'{a}bc}{\result} Initial: \result. 

\emph{ábc}: \DTLGetInitialLetter{\emph{ábc}}{\result} Initial: \result. 

Purify late.\DTLsetup{initial-purify=late} 

\'{a}bc (accent command): \DTLGetInitialLetter{\'{a}bc}{\result} Initial: \result. 

\emph{ábc}: \DTLGetInitialLetter{\emph{ábc}}{\result} Initial: \result. 
\end{document}