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The prevention of dental caries and periodontal diseases is targeted at the control of dental plaque. In this context, chemical agents could represent a valuable complement to mechanical plaque control. The active agents should prevent biofilm formation without affecting the biological equilibrium within the oral cavity. Depending on the goals of the preventive measures, various strategies may be considered. Anti-plaque agents with properties other than bactericidal or bacteriostatic activities may be used in primary prevention. In this approach, a modest anti-plaque effect may be sufficient or even desirable, as it would decrease the side effects of the active agent. Antimicrobial agents are best indicated in secondary and tertiary prevention, as the objectives are to restore health and to prevent disease recurrence. The rational is to prevent or delay subgingival recolonization by pathogenic micro-organisms. The development of in vitro oral biofilm models certainly represents a major advance for studying and testing oral anti-plaque agents in recent years. The results of these studies have shown that chlorhexidine, hexetidine, delmopinol, amine fluoride/stannous fluoride, triclosan, phenolic compounds, among others, may inhibit biofilm development and maturation as well as affect bacterial metabolism.