Conspectus
Interaction
between nanomaterials (NMs) and biological systems
can be beneficial for biological functions but also can present hazards
to humans. Nanotoxicology and nanomedicine, as two subdisciplines
of nanotechnology, share the same goal of making safer NMs for biomedical
application. NMs with unique electronic properties have been widely
used for biomedical applications, such as bacterial inactivation,
wound healing, tumor therapy, and Alzheimer’s disease therapy.
Meanwhile, the biosafety of NMs has become a hot topic, and development
of effective “safe-by-design” strategies will be beneficial
for the wide applications of NMs in the biomedical field. However,
it is currently hard to establish a property–activity relationship
between NMs and their biosafety and biomedical applications, especially
for electronic band structure including conduction band energy (E
c), valence band energy (E
v), Fermi energy (E
f), and bandgap
energy (E
g). E
g determines the suitable lights used to excite NMs, and E
c and E
v determine the redox
abilities of photoinduced electrons and holes, while E
f dominates the charge transfer process within NMs. Therefore,
through modulating the electronic band structure of NMs, not only
can the biosafety of NMs be elevated, but also the photoelectronic
performance can be improved, providing a profound understanding to
the design of functional NMs for the biomedical application with excellent
biocompatibility.
In this account, we focus on our recent progress
in electronic
band structure-modulated NMs for biosafety and biomedical application.
First, we investigate the toxicities of NMs with different E
c levels and establish safe-by-design strategies
to make safer NMs through modulating their electronic properties,
such as tuning E
c values of NMs out of
the biological redox potential range and tuning the E
f edge far away from the E
v edge. Second, we propose that deep level defect, resonance energy
transfer, and narrow band gap intensely correlate with the photothermal
performance of NMs and rationally designed heterostructures can significantly
improve the photothermal conversion efficacies of these NMs. Third,
we introduce a series of NMs with unique heterostructure to promote
photoinduced electron–hole spatial separation and improve photodynamic
performance for antibacterial and anticancer applications. Among these
heterostructures, the thermally retractable heterostructure can create
a favorable microenvironment for photodynamic therapy; Z-scheme heterostructure
can simultaneously produce oxygen and reactive oxygen species for
photodynamic therapy against hypoxic tumor; plasmon–pyroelectric
heterostructure can thermally generate reactive oxygen species in
an oxygen-independent manner for hypoxic tumor therapy. Furthermore,
we describe the photooxidation and antioxidant abilities of NMs for
treating Alzheimer’s disease through inhibiting amyloid-β
self-assembly and scarifying reactive oxygen species. Finally, we
propose the challenges and perspectives of electronic band structu...