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Reliable, real-time, in vivo sensing (intravascular) of blood gases and electrolytes remains a difficult challenge owing to biocompatibility issues that occur when chemical sensors are implanted into the blood stream. Recently, local release of nitric oxide (NO) at the sensor/blood interface has been suggested as a potential solution to this problem. However, the lifetime of NO release from thin polymer films coated on implanted sensors is limited by the reservoir of NO donor loaded within the polymeric coating. To continuously produce NO at the sensor/blood interface, a novel approach to catalytically decompose endogenous S-nitrosothiols (RSNOs) in blood to generate NO in situ is reported herein. Metallic copper particles of two different sizes (3 μm and 80 nm) are embedded as catalysts in thin polymer coatings on the surface intravascular electrochemical oxygen sensing catheters. Oxygen levels (partial pressure of oxygen; PO(2)) provided by the copper particle/polymer coated sensors are, on average, more accurate than values obtained from non-NO generating control sensors when both types of sensors are implanted in porcine arteries for 19-20 h. Upon termination of each in vivo study, catheters were explanted and examined for surface thrombosis via both visual image and lactate dehydrogenase (LDH) assay. The results indicate that the Cu(0)-catalyst coatings significantly reduce the occurrence of surface thrombosis, likely from the ability to generate NO from endogenous RSNO species at the sensor/blood interface.