Many proteins form noncovalent and thermodynamically reversible oligomers, and the state of self-association can dictate a proteins functionality. DNA-binding proteins are very often dimeric, while other proteins exist as trimers (e.g. chloramphenicol transacetylase), tetramers (e.g. hemoglobin), or higher-order reversible association products (tubulin, viral coat proteins, sickle cell hemoglobin), with clear functional roles that have never been observed for carbohydrates. Although weak self-association in a polysaccharide has been shown, [1] we show for the first time the presence of multiple oligomeric forms in a whole class of polymeric carbohydrates, 6-deoxy-6-aminocelluloses, using the hydrodynamic technique of analytical ultracentrifugation as a probe.Water-soluble aminocelluloses were prepared by the reaction of tosyl cellulose with an excess of di-or trifunctional amines, namely with tris(2-aminoethyl)amine yielding 6-deoxy-6-(2-(bis(2-aminoethyl)aminoethylamino) (BAEA) cellulose (1-3), as depicted in Figure 1. Similar structures were obtained from reactions of tosyl cellulose with 1,2-diaminoethane and 4,7,10-trioxa-1,13-tridecandiamine to give 6-deoxy-6-(2-aminoethyl)amino (AEA) cellulose 4 and 6-deoxy-6-(13-amino-4,7,10-trioxatridecaneamino) (ATOTA) cellulose 5, respectively (Supporting Information Figure 1). The degree of substitution (DS) ranged from 0.60 to 0.85 (Supporting Information Table 1). NMR spectroscopic studies revealed that the nucleophilic displacement takes place at the primary position 6 of the anhydroglucose unit (AGU). [2] Sedimentation coefficient distributions for the five different 6-deoxy-6-aminocelluloses were obtained from sedimentation velocity experiments in the analytical ultracentrifuge for six different solute loading concentrations (from 0.125 to 2.0 mg mL À1 ) in 0.1m phosphate-buffered saline (pH 6.8). Astonishingly, for every aminocellulose studied, the sedimentation coefficient distributions show between four and five discrete species with a stepwise increase in sedimentation coefficient. For example, the lowest sedimentation coefficient of the BAEA cellulose 1, prepared from cellulose with a degree of polymerization (DP) of 450, was detected at 1.8 Svedbergs (S). Additional species sedimenting at peak maxima of approximately 2.8, 4.0, 5.1, and 6.5 S were also clearly found using the SEDFIT algorithm of Dam and Schuck [3] (Figure 1). The measurements were repeated for two other BAEA celluloses prepared from cellulose with DP = 250, and comparable results were obtained (Figure 2 b, c). Peaks with sedimentation coefficients of approximately 1.6, 2.3, 3.1, 4.3, and 5.3 S have been found for an AEA cellulose (4) prepared from cellulose with DP = 450. Furthermore, the ATOTA cellulose 5 shows peaks sedimenting with maxima at approximately 1.7, 2.9, 4.3, and 5.5 S (Figure 2; Supporting Information Table 2). To check that the peaks were not artifacts of the analysis procedure, least-squares g(s) versus s distribution data were also obtained (Supporting Information Figure 3 a...