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As the μ opioid receptor (MOR) endogenous tetrapeptides,endomorphin-1 (EM-1:H-Tyr-Pro-Trp-Phe-NH2) has attracted much attention from the peptide chemist/pharmacologist teams,and has been considered as useful pharmacological tools with tremendous potential in pain alleviation.Recently,a novel series of unnatural α-methylene-β-amino acids (Map) were incorporated into EM-1 as a replacer of Phe4.