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We review the growing field of entrapment of purified enzymes, whole cells, antibodies, and other proteins in sol-gel matrices prepared from metal alkoxides. Basic aspects of the nature of the trapping and its effects on the dopant activity are discussed, andvarious applicative uses of these novel bioactive materials are presented, including sensors, biosensors, electrodes, immunoadsorbents, optical components, environment-related materi-als, and biotechnology-relatedmaterials. Outlook of potential applications and future directions of this field are provided throughout the review.