Measurement of the molecular weight of micelles, which are characteristic aggregates of molecules, was conducted using electrospray ionization mass spectrometry (ESI-MS). Micelle solutions were prepared by dissolving octyltrimethylammonium bromide [OTAB: C 8 H 17 N(CH 3 ) 3 Br] in water alone, without other additives. From the measurement of the m/z of the doubly or triply charged ions, it was revealed that the micelle of OTAB exhibited an almost symmetrical and polydisperse distribution about the mean molecular weight of 5000-5500. This molecular weight information is in good accordance with other estimated values. This result demonstrated the possibility of a direct measurement of micelle weight by mass spectrometry. # 1998 John Wiley & Sons, Ltd. Received 17 August 1998; Revised 5 October 1998; Accepted 7 October 1998 Recently, molecular aggregates associated by noncovalent interactions have been actively studied regarding their function, structure, and the interaction associating them.
Electrospray ionization (ESI)1,2 has made it possible to directly measure the molecular weight of biopolymer accurately by producing multiply charged ions from the solution phase.3,4 Furthermore, molecular aggregates 5 due to noncovalent interactions can be detected under the prevailing conditions of ESI because it is a soft ionization technique. A variety of investigations using ESI have reported aggregates such as protein-ligand, 6-9 enzymesubstrate or enzyme-inhibitor, 10,11 protein-protein, protein-peptide, or peptide-peptide 12-15 and antibioticsligand. 16 Various methods have been employed in the measurement of the molecular weight of the micelle that is produced by these characteristic aggregations of relatively small molecules, e.g., light-scattering spectrometry, gel-filtration liquid chromatography and viscosity measurement. These can offer the mean molecular weight and the weight distribution, calculated on the basis of an hypothesis or the rough molecular weight by adaptation of a suitable calibration curve prepared from standard samples. This communication demonstrates the possibility of the measurement of micelle weight by ESI-MS. The successful application of the mass spectrometer to the direct measurement of micelle weight may open up a new field in the research of molecular aggregates.
EXPERIMENTAL MaterialsThe micelle solution was prepared by dissolving octyltrimethylammonium bromide (OTAB) in distilled deionized water, without any additives. The concentration of OTAB was 0.56 M which was four times the critical micelle concentration (CMC) of this surfactant.
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Mass spectrometryThe mass spectrometer used was of sector type (JMS-AX505HA, JEOL, Tokyo) equipped with an ESI ion source (Analytica of Branford, Branford, CA). The ionization voltage of 3.5 kV was applied to the outlet of the stainless steel nozzle. The micelle solution was infused by a syringe pump at the constant flow rate of 1 mL min À1 .
RESULTS AND DISCUSSIONThe change in bias imposed between capillary and skimmer (DCS), in the ion source, can...