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Recent studies have shown that use of direct current arc plasma jet is a promising technique for bulk generation of nanostructures. This paper presents a dynamical study on such systems during the synthesis and attempts to correlate the role of inherent arc fluctuations on the properties of nanostructures produced. Different fluctuations detected during the process of nanosynthesis have been characterized in terms of behavior in real time, phase space, frequency space, fractal dimension, Lyapunov exponent of evolution and diagnosed to be chaotic. For the first time, it has been shown that size of nanoparticles are strongly related to the Lyapunov exponent of inherent voltage fluctuations realized during the synthesis. Interesting features of such dependences under different process conditions have been brought out. Since chaotic systems are controllable, the study brings out the possibility of development of new size control strategies for nanosynthesis.