Using a novel method of isochronous mass spectrometry, the masses of , , , and are measured for the first time, and the masses of , , , , , , and are redetermined with improved accuracy. The new masses allow us to derive residual proton-neutron interactions () in the nuclei, which are found to decrease (increase) with increasing mass for even-even (odd-odd) nuclei beyond . This bifurcation of cannot be reproduced by the available mass models, nor is it consistent with expectations of a pseudo-SU(4) symmetry restoration in the shell. We performed ab initio calculations with a chiral three-nucleon force (3NF) included, which indicate the enhancement of the pairing over the pairing in this mass region, leading to the opposite evolving trends of in even-even and odd-odd nuclei.