Conspectus
The development of in vivo analytical
tools and methods for recording electrical signals and accurately
quantifying chemical signals is a key issue for a comprehensive understanding
of brain events. The electrophysiological microelectrode was invented
to monitor electrical signals in free-moving brains. On the other
hand, electrochemical assays with excellent spatiotemporal resolution
provide an effect way to monitor chemical signals in vivo. Unfortunately,
the in vivo electrochemical biosensors still have three limitations.
First, many biological species such as reactive oxygen species (ROS)
and neurotransmitters demonstrate large overpotentials at conventional
electrodes. Thus, it is hard to convert the chemical/electrochemical
signals of these molecules into electric signals. Second, the interfacial
properties of the recognition molecules assembled onto the electrode
surfaces have a great influence on the transmission of electric charge
through the interface and the stability of the modified recognition
molecules. Meanwhile, the surface of biosensors implanted in the brain
is easily absorbed by many proteins present in the brain, resulting
in the loss of signals. Finally, activities in the brain including
neuron discharges and electrophysiological signals may be affected
by electrochemical measurements due to the application of extra potentials
and/or currents.
This Account presents a deep view of the fundamental
design principles and solutions in response to the above challenges
for developing in vivo biosensors with high performance while meeting
the growing requirements, including high selectivity, long-time stability,
and simultaneously monitoring electrical and chemical signals. We
aim to highlight the basic criteria based on a double-recognition
strategy for the selective biosensing of ROS, H2S, and
H
n
S through the rational design of specific
recognition molecules followed by electrochemical oxidation or reduction.
Recent developments in designing functionalized surfaces through a
systematic investigation of self-assembly with Au–S bonds,
Au–Se bonds, and AuC bonds for facilitating electrochemical
properties as well as improving the stability are summarized. More
importantly, this Account highlights the novel methodologies for simultaneously
monitoring electrical and chemical signals ascribed to the dynamic
changes in K+, Na+, and Ca2+ and
pH values in vivo. Additionally, SERS-based photophysiological microarray
probes have been developed for quantitatively tracking chemical changes
in the live brain together with recording electrophysiological signals.
The design principles and novel strategies presented in this Account
can be extended to the real-time tracking of electrical signals and
the accurate quantification of more chemical signals such as amino
acids, neurotransmitters, and proteins to understand the brain events.
The final part also outlines potential future directions in constructing
high-density microarrays, eventually enabling the large-scale dynamic
recording of the chemical e...