You can use np.fromiter to directly create numpy arrays from the dictionary key and values views:
In python 3:
keys = np.fromiter(Samples.keys(), dtype=float)
vals = np.fromiter(Samples.values(), dtype=float)
In python 2:
keys = np.fromiter(Samples.iterkeys(), dtype=float)
vals = np.fromiter(Samples.itervalues(), dtype=float)