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Biomolecules, especially large polymeric molecules such as enzymes and antibodies, mediate various biological functions, including biochemical reactions and molecular recognition, with high reactivity, efficiency, selectivity and accuracy. Many researchers have investigated methods to take advantage of these characteristics in analytical devices. One way to accomplish this is to immobilize biomolecules in the devices. For example, biomolecules have been immobilized by means of silica sol-gel technology and used for basic research in the food and pharmaceutical industries. Proteins encapsulated by this method retain their structure and biological activity for a prolonged period. This review describes methodologies for immobilization of biomolecules and the applications of sol-gel technology to analytical devices, especially flow-through systems.