Supplementary material from "The atypically high modulus of pollen exine"

Sporopollenin, the polymer comprising the exine (outer solid shell) of pollen, is recognized as one of the most chemically and mechanically stable naturally occurring organic substances. The elastic modulus of sporopollenin is of great importance to understanding the adhesion, transport and protective functions of pollen grains. In addition, this fundamental mechanical property is of significant interest in using pollen exine as materials for drug delivery, reinforcing fillers, sensors and adhesives. Yet, the literature reports of sporopollenin modulus are very limited. We provide the first report of the elastic modulus of sporopollenin from direct indentation of pollen particles of three plant species: ragweed (Ambrosia artemisiifolia), pecan (Carya illinoinensis) and Kentucky bluegrass (Poa pratensis). Modulus was determined with atomic force microscopy by using direct nanomechanical mapping of the pollen shell surface. The moduli were atypically high for non-crystalline organic biomaterials, with average values of 16 ± 2.5 GPa (ragweed), 9.5 ± 2.3 GPa (pecan) and 16 ± 4.0 GPa (Kentucky bluegrass). The amorphous pollen exine has a modulus exceeding known non-crystalline biomaterials, such as lignin (6.7 GPa) and actin (1.8 GPa). In addition to native pollen, we have investigated the effects of exposure to a common preparative base–acid chemical treatment and elevated humidity on modulus. Base–acid treatment reduced the ragweed modulus by up to 58% and water vapour exposure at 90% relative humidity reduced the modulus by 54% (pecan) and 72% (Kentucky bluegrass). These results are in agreement with recently published estimates of the modulus of base–acid-treated ragweed pollen of 8 GPa from fitting to mechanical properties of ragweed pollen–epoxy composites.