The physical chemical behavior of a series of N-alkyl amino acid-based surfactants has been investigated. The series comprises four different types of amino acids as polar headgroups: glycine, aminomalonic acid, aspartic acid and glutamic acid, and for each type three homologues were synthesized: the octyl, decyl and dodecyl derivative. Aminomalonic acid, aspartic acid and glutamic acid are dicarboxylic amino acids with one, two and three methylene groups as spacer between the carboxylic groups, respectively. Compared with the more common N-acyl surfactants based on the same amino acids, many of the N-alkyl derivatives exhibited relatively high Krafft temperatures. The N-alkyl derivatives also had considerably lower critical micelle concentrations (CMCs) and they gave low values of surface tension at the CMC. The length of the spacer between the two carboxylic groups did not much influence the micellization. Some of the surfactants, in particular the lower homologues of N-alkylglycinate surfactants, gave unusually low surface tension values. The low values are most likely due to formation of a mixed monolayer at the surface, comprising of alternating anionic N-alkylglycinate and cationic N-protonated-N-alkylglycine. In a plot of conductivity vs. surfactant concentration there was no kink on the curve around the CMC, as determined by tensiometry. The absence of such a kink is in accordance with the view that self-assembly of the N-alkyl amino acid-based surfactants involves formation of mixed micelles consisting of alternating N-alkyl amino acid anion and N-protonated-N-alkyl amino acid also in the bulk solution. The protonation of the N-alkyl amino acid anion, which generates hydroxyl ions, is driven by the energetically favorable formation of mixed micelles consisting of anionic and cationic amphiphiles. (C) 2013 Elsevier Inc. All rights reserved.