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This study reports on new pharmacologically active endomorphin-2 analogues, incorporating β2-hPhe, β3-hPhe and β3-hTic unnatural amino acids in the place of the Phe3–Phe4residues. Such α, β-hybrid analogues were designed to exploit the great potential of β-amino acids in generating conformational variation at the key positions 3 and 4, with the aim of evaluating the effect on the opioid binding...