01 - Preheat oven to 375°F. Grease a standard 12-cup muffin tin generously with butter or line with paper liners.
02 - In a medium bowl, toss together the diced rhubarb, ½ cup granulated sugar, and 2 tablespoons melted butter until the rhubarb is evenly coated. Spoon a heaping tablespoon of the mixture into the bottom of each muffin cup, pressing gently to form an even layer.
03 - In a large mixing bowl, whisk together the flour, remaining ½ cup sugar, baking powder, baking soda, and salt until well blended.
04 - In a separate bowl, whisk the cooled melted butter, egg, buttermilk, and vanilla extract until smooth and fully incorporated.
05 - Pour the wet mixture into the dry ingredients and fold together gently with a spatula just until no dry streaks remain. Take care not to overmix, as this will produce tough muffins.
06 - Divide the batter evenly among the 12 muffin cups, spooning it directly over the rhubarb layer. Smooth the tops lightly.
07 - Bake on the center rack for 22 to 25 minutes, rotating the pan halfway through, until a toothpick inserted into the center of a muffin comes out clean.
08 - Let the muffins rest in the pan for 5 minutes. Run a butter knife around the edges of each muffin, then carefully invert the pan onto a wire rack so the rhubarb side faces up. Serve slightly warm or at room temperature.