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PROTOCOL
558 | VOL.10 NO.4 | 2015 | NATURE PROTOCOLS
INTRODUCTION
Symmetry and chirality are properties commonly found through-
out the natural world. Chirality is one of the most important
factors in molecular recognition, with chiral compounds having a
major role in chemistry, biology and medicine. Chirality has also
been envisaged to have an important role in nanotechnology
1–6
,
and an understanding of the fundamental concepts relevant to chi-
rality in nanosystems is important for the further advancement of
nanoscience in general and for nanobiotechnology in particular.
Over the past years, the research on chiral metal nanoparticles
has received a great deal of attention owing to the range of poten-
tial applications offered by these materials as chiral sensors, cata-
lysts and as metamaterials in advanced optical devices
1–3,7–11
. The
use of stereospecific chiral stabilizing molecules has also opened
up another avenue of interest in the area of QD research. Optically
active chiral QDs (penicillamine-stabilized CdS) were first pre-
pared by our group by using microwave-induced heating with
the racemic (Rac), D- and L-enantiomeric forms of penicillamine
used as stabilizers
12
. It was found that these QDs demonstrated
very broad luminescence bands (between 370 and 710 nm), which
are attributed to defects or electron-trap states on the surface of
the nanocrystals. Importantly, a clear relationship between lumi-
nescence that originated by defects and circular dichroism (CD)
activity was observed for CdS chiral QDs. Our density functional
calculations of the electronic states have demonstrated that CD
at longer wavelengths is associated with near-surface cadmium
atoms that are enantiomerically distorted by chiral penicillamine
ligands, which translate their enantiomeric structure to the sur-
face layers and associated electronic states, whereas the QD core
is found to remain undistorted and achiral
13
.
After that work, we later reported the preparation of chiral CdSe
(ref. 14), CdTe (refs. 15,16) and chiral CdS nanotetrapods
17
. All of
these chiral nanostructures showed characteristic CD responses
within the band-edge region of their UV-visible spectrum, as well
as very broad distribution of photoluminescence (PL), which
originates from emissive defect states. The concept of chiral
surface defects of QDs (distorted QD shell) was also confirmed
by other groups with CdTe nanocrystals bearing various chiral
ligands
18–20
. Interestingly, it was shown that the chirality of the
QD surface was maintained even after ligand exchange with an
achiral thiol and subsequent transfer of the CdTe QDs into a
different (organic) phase. In this case, chiral QDs have shown a
unique ‘chiral memory’ effect
19
.
However, chirality in chiral QDs can be caused not necessar-
ily only by chiral surface defects but also by other factors. For
example, the effects of cysteine enantiomers on optical isomerism,
growth rate and structure of chiral CdTe–based QDs was reported
by Kotov and colleagues
20
. This paper postulated that the atomic
origin of chiral sites in nanoparticles is geometrically similar to
that in organic compounds. By using theoretical calculations and
experimental data, the researchers showed that atoms in chiral
cysteine–stabilized CdTe nanocrystals are arranged as tetrahe-
drons, and that chirality occurs when all tetrahedral apexes have
chemical differences and substitution
20
.
More recently, chiral ligand–induced CD in CdSe QDs was
reported by Balaz and colleagues
21,22
. The researchers have found
that a simple phase transfer of trioctylphosphine oxide or oleic
acid–capped CdSe QDs from toluene into aqueous phase using
chiral thiol capping ligands such as L- and D-cysteines can induce
chiroptical properties in originally achiral cadmium selenide QDs.
In addition, it was shown that L- or D-cysteine-stabilized QDs in
aqueous phase demonstrated size-dependent electronic CD and
chiral ligand–induced circularly polarized luminescence in QDs. In
this case, the authors have explained the origin of the induced CD
in QDs by the hybridization of the chiral ligand’s highest occupied
molecular orbitals (HOMOs) with CdSe molecular orbitals
21
.
The literature data above clearly demonstrate that chiral sta-
bilizing ligands and induced chirality effects have a crucial role
in the properties and behavior of chiral QDs, enabling a range
of potential applications for these nanomaterials in chemistry,
nanotechnology and biology.
One important application of chiral QDs is luminescence sens-
ing and chiral recognition of enantiomers
18,23,24
. A fundamental
Preparation of chiral quantum dots
Mícheál P Moloney
1
, Joseph Govan
1
, Alexander Loudon
1
, Maria Mukhina
2
& Yurii K Gun’ko
1,2
1
School of Chemistry and Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN) Institute, Trinity College Dublin, Dublin, Ireland.
2
Center of Information Optical Technologies, Information Technologies, Mechanics and Optics (ITMO) University, Saint Petersburg, Russia. Correspondence should
be addressed to Y.K.G. (igounko@tcd.ie).
Published online 5 March 2015; doi:10.1038/nprot.2015.028
Chiral quantum dots (QDs) are expected to have a range of potential applications in photocatalysis, as specific antibacterial and
cytotoxic drug-delivery agents, in assays, as sensors in asymmetric synthesis and enantioseparation, and as fluorescent chiral
nanoprobes in biomedical and analytical technologies. In this protocol, we present procedures for the synthesis of chiral optically
active QD nanostructures and their quality control using spectroscopic studies and transmission electron microscopy imaging.
We closely examine various synthetic routes for the preparation of chiral CdS, CdSe, CdTe and doped ZnS QDs, as well as of chiral CdS
nanotetrapods. Most of these nanomaterials can be produced by a very fast (70 s) microwave-induced heating of the corresponding
precursors in the presence of D- or L-chiral stabilizing coating ligands (stabilizers), which are crucial to generating optically
active chiral QDs. Alternatively, chiral QDs can also be produced via the conventional hot injection technique, followed by a phase
transfer in the presence of an appropriate chiral stabilizer. We demonstrate that the properties, structure and behavior of chiral QD
nanostructures, as determined by various spectroscopic techniques, strongly depend on chiral stabilizers and that the chiral effects
induced by them can be controlled via synthetic procedures.