DNA is a way to store data. It doesn't specifically "operate" in base 4 because the DNA replication doesn't use mathematics - it just replicates, the only logic involved is the pair forming of the four bases. DNA is a continuous data block that just happens to use four different bases (in CHEMICAL context) as its method of storing the protein encoding instructions. Making a logical operator that uses DNA would be quite hard (and would likely require use of RNA to modify the DNA sequences), but as memory, DNA would be better suited. I am unfamiliar with the proposed DNA computers' principles, so I won't say any more on that subject.
Human brain, on the other hand, is a neural net with binary signals, but much more complicated than binary logic. The signals are either on/off (electric potential opens calcium ion gates between nerve cells and electric potential pulses travel through synapses, not as electrons like in metallic conductors, but as ions more similar to what you have if you put two types of electrolytes in two glasses and connect them with a wetted paper strip, and then put anode in one glass and cathode in the other glass; you can run current through the wetted paper strip in form of ions traveling through it.
The neural network formed by nerve cells and their connections is, then, hooked to a LOT of input/output nodes, and is largely dependant on those inputs and outputs to function properly and meaningfully (sensory deprivation is a very nerve-wracking situation, literally). And while individual nerve signals are on/off variety, the brain still interpretes sensory input as largely analog signals, depending on how many nerve endings are sending the same signal, in which case the signal amplitude increases. Each brain is has similar parts, such as the main input/output lines up to the spinal chord and brain stem, and their direct handling areas (for example visual cortex is roughly similar in structure for each person and in roughly same location, too), but each brain is also individually structured based on genetics and the experiences forming new neural pathways.
The resulting jumble of nerve signals results in personality and consciousness, but it cannot really be looked as analogous to a "computer" as we see it. There are a lot of parts in the brain that do tasks similar to "computing" - most of it subconscious routines such as breathing or hormone control, as well as balance handling which affects things like motion control, image stabilization, eye tracking, and a lot more. But even then these subroutines can't really be thought of as binary computers that get input values from senses and send output values accordingly; it's more of an analogous system that has assembled to respond to stimuli in a way that produces certain results.
It would be expected that a neural network assembled with evolutionary algorithms would become largely similar system, with no specific designed features, but instead stuff that just works as needed.