- Using a surface forces apparatus, we have investigated the adhesive and lubrication forces of mica surfaces separated by a molecularly thin, subnanometer film of a high-molecular-weight (2.3 MDa) anionic polysaccharide from the algae Porphyridium sp. adsorbed from aqueous solution. The adhesion and friction forces of the confined biopolymer were monitored as a function of time, shearing distance, and driving velocity under a large range of compressive loads (pressures). Although the thickness of the dilute polysaccharide was <1 nm, the friction was low (coefficient of friction = 0.015), and no wear was ever observed even at a pressure of 110 atm over 3 decades of velocity, so long as the shearing distances were less than twice the contact diameter. Atomic force microscopy in solution shows that the biopolymer is able to adsorb to the mica surface but remains mobile and easily dragged upon shearing. The adhesion (adsorption) of this polysaccharide even to negatively charged surfaces, its stable low friction, its robustness (high-load carrying capacity and good wear protection), and the weak (logarithmic) dependence of the friction force on the sliding velocity make this class of polyelectrolytes excellent candidates for use in water-based lubricant fluids and as potential additives to synovial fluid in joints and other biolubricating fluids. The physical reasons for the remarkable tribological properties of the ultrathin polysaccharide monolayer are discussed and appear to be quite different from those of other polyelectrolytes and proteins that act as thick “polymer brush” layers.