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In this quote, Ambrose Bierce is taking a cynical view of philanthropists. By describing a philanthropist as a “rich old gentleman” who has trained himself to “grin” or smile while his “conscience is picking his pocket”, Bierce suggests that some philanthropic acts are not truly altruistic or done out of genuine care for others in need.
He implies that for some philanthropists, donating to charitable causes is a way to ease their conscience about accumulating wealth, while also providing further tax breaks or positive publicity. So in essence, Bierce is accusing certain philanthropists of using donations as a way to feel better about themselves and their wealth, rather than coming from pure, selfless motivations to help the less fortunate.