Atmospheric plasma treated carbon fiber filaments (10 micrometer) were used as the base substrate in the design of a probe intended for use within intravascular access devices. The microfiber probe was further functionalized with a polyplumbagin layer through which the line pH could be determined voltammetrically and therein provide the potential for obtaining diagnostic information relating to bacterial colonization of the line. The redox processes attributed to the immobilized polymer are characterized and a methodology developed to enable the acquisition of a redox signal that is selective and sensitive to pH. The applicability of the composite probe was demonstrated through examining the direct response in whole blood.