The B vitamins release and metabolize fat, carbs, and protein into energy. So taking them would release energy from fats and carbs, instead of them being stored.
The reason B5 helps with skin is because if taken as high doses, it will turn the oil in your face into energy rather than being released through your pores, since oil is a fat. But, you'd have to take high doses of B5, 3-10g a day, which can be costly... The average size is 500mg and 100 tablets. You can't really overdose on B5 since its water-soluble and whatever isnt used will be in your urine. The only side-effect I've heard of high doses is diarrhea...
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