Glycogen, a hyperbranched complex glucose polymer, is involved in regulating blood-glucose levels in the body. Liver glycogen comprises complex α particles made of smaller β particles joined together. The recent discovery that α particles are smaller and fewer in diabetic, compared to healthy, mice highlights the need to elucidate the nature of α-particle binding. Examining changes in α-particle size (using several different techniques) with various reagents that disrupt different types of bonds suggest that this binding is due to neither disulfide nor hydrogen bonds, nor hydrophobic interactions, but there was an effect with acid hydrolysis. This suggests that α particles are linked together by protein and not via glycosydic linkages; this has potential application in novel drug targetting to mitigate diabetes.