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Spray six 3/4-cup ramekins with a light coating of cooking spray. Or prepare panna cotta in a 1-quart serving bowl without cooking spray.
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Sprinkle gelatin over cold water in a small bowl. Let stand until softened.
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Heat heavy cream, 1/2 cup sugar and orange zest in a medium saucepan over medium-high heat to just below boiling; stir until sugar dissolves.
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Remove from heat. Add gelatin mixture and stir until dissolved. Cool to lukewarm.
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Stir buttermilk and vanilla into cream mixture. Divide evenly between prepared ramekins or pour into bowl.
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Refrigerate 4 hours or until set. (Can be covered and refrigerated up to 48 hours ahead.)
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Combine blackberries, Cointreau and remaining 2 teaspoons sugar in a medium bowl. Using the back of a spoon or a fork, gently mash berries, leaving some of the berries whole.
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To serve, run the tip of a sharp knife around edge of ramekins.
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Turn out onto serving plates. (Or scoop panna cotta into dessert dishes). Spoon berries alongside or on top of panna cotta.