Visual enantioselective probe based on metal organic framework incorporating

quantum dots
Zhou Long, Jia Jia, Shanling Wang, Lu Kou, Xiandeng Hou, Michael J.
Sepaniak
PII:
DOI:
Reference:

S0026-265X(13)00154-9
doi: 10.1016/j.microc.2013.08.013
MICROC 1818

To appear in:

Microchemical Journal

Received date:
Accepted date:

20 August 2013
24 August 2013

Please cite this article as: Zhou Long, Jia Jia, Shanling Wang, Lu Kou, Xiandeng Hou, Michael J. Sepaniak, Visual enantioselective probe based on metal organic framework incorporating quantum dots, Microchemical Journal (2013), doi:
10.1016/j.microc.2013.08.013

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Visual enantioselective probe based on metal organic

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framework incorporating quantum dots

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Zhou Longa, Jia Jiaa, Shanling Wanga, Lu Koub, Xiandeng Hou*a,b, Michael J.

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Sepaniak*c

Analytical & Testing Centre, Sichuan University, Chengdu, Sichuan 610064, China.

College of Chemistry, Key Laboratory of Green Chemistry and Technology of MOE at

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Sichuan University, Chengdu, Sichuan 610064, China.

Department of Chemistry, The University of Tennessee, Knoxville, TN-37996-1600,

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U.S.A.

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Abstract

A new method was developed for visual enantioselective sensing based on quantum
dots (QDs) doped metal organic framework (MOF), which firstly combined the chiral

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selectivity of MOF and sensing of QD quenching. A simple synthesis procedure with

much less reaction time is developed, with small and homogenously-sized QD@MOF
particles obtained, as well as a cheaper dispersant used. The proposed sensing method
is proved to be direct, convenient, and visual. Qualification and preliminary
quantification of enantiomers can be accomplished in a visual fashion. The proposed
method also demonstrates practical utility, and it is expected to be expanded to
enantioselective determination of other enantiomers.
Keywords: Metal organic framework; quantum dots; visual enantioselective sensing.

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1. Introduction

The study of chiral recognition has received compelling attention in recent years, which

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is very important to the understanding of rational of asymmetric synthesis [1] or

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catalysis [2], and the development of chiral separation [3] and sensing [4]. During the
past few years, considerable efforts have been devoted to the development of simple,

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effective and low-cost enantioselective sensors [5], while the design of visual
discrimination of enantiomers, which is more convenient, direct, and low-cost for no

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analytical instrument needed, still remains challenging. By present, only a few examples
of visual chiral recognition have been reported, by discernable colour change or

precipitate formation caused by the interactions between target enantiomers and the

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sensing platforms using modified nanoparticles [6] or gels [7]. Further exploration of

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this research field is thus highly in demand.

In this context, we proposed the first visual chiral fluorescence (FL) sensor employing
metal organic framework (MOF) with quantum dot (QD) caged inside. Since last

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decade, FL probes involving QDs have been employed for bio/chemical sensing [8],
following the turn-off mechanism through FL quenching of QDs caused by the
interaction between QDs and target analytes [9]. The broad absorption band in the
visible region of QDs makes it easy to achieve visual sensing [10]. MOFs are extended
crystalline structures wherein metal cations or clusters of cations are connected by
multitopic organic strut or linker ions or molecules [11], and they have already been
used in asymmetric catalysis [12], separation [13] and chromatography [14]. Moreover,
its intrinsic chiral topology, cavity confinement effect and conformational rigidity,
make MOF become an ideal sensing platform for chiral recognition. Up to now, only a

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few examples concerning MOF-based enantioselective sensors have been reported [15],
but the research goal of visual chiral recognition employing MOF has rarely been

realized. Buso et al. [16] lately incorporated QD within MOF for visual molecular

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discrimination based on molecular size, but a high level of visual chiral specificity

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needs to be achieved by both shape and size selectivity, which will be accomplished by

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the work presented herein.

2. Materials and Methods

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2.1. Apparatus

The microwave reactor (Uwave-1000) was purchased from Sineo Microwave Chemistry

Technology (Shanghai, China). The microwave working frequency was at 2450 MHz

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and the probe ultrasonic working frequency was between 26-28 KHz. The FL data were

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collected from an F-7000 FL Spectrometer (Hitachi, Japan) with a 390 nm optical filter.
The powder X-ray diffraction (PXRD) patterns were obtained from an X'Pert Pro MPD
(Philips, Netherlands) using Cuka radiation. The scanning electron microscopy (SEM)

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images were obtained from a JEOL model JSM-7500F scanning electron microscope.
The transmission electron microscopy (TEM) images were obtained from an FEI Tecnai
G2 F20 S-TWIN transmission electron microscope.

2.2. Reagents
All of the chemicals used are AR grade. Ultrapure water (18.25 Mcm) produced with
a purification water machine (PCWJ-10, Pure Technology Co. Ltd, Chengdu, China)
was used throughout this work. Sodium tellurite, mercaptopropionic acid, D- and Ltartaric acid, D- and L-dimethyl tartrate, D- and L-mandelic acid, were purchased from

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Aladdin Reagents Co.,Ltd. (Shanghai, China), CdCl22.5H2O, trisodium citrate

dehydrate, NaBH4, N, N-Dimethylformamide (DMF), Zn(NO3)26H2O and ethanol were

obtained from Kelong Chemical Reagent Co. Ltd. (Chengdu, China); D-camphoric acid

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and 4, 4-dipyridyl were ordered from Juhui Chemical Reagent Co. Ltd. (Chengdu,

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China). All chemicals and standards were kept at 4 oC in a refrigerator until use.

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2.3. Synthesis of CdTe QDs (QDs)

The QDs were prepared with a procedure similar to the one-pot synthetic method

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reported previously [17]. 0.5 mmol CdCl22.5H2O and 200 mg trisodium citrate
dehydrate were dissolved in 50 mL water, followed by instant addition of 52 L

mercaptopropionic acid (MPA). The pH of the solution was adjusted to 10.5, followed

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by the addition of 0.1 mmol Na2TeO3 and 50 mg NaBH4. The solution was then placed

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in a microwave reactor set at 100 oC to produce the QDs capped with MPA, with no
extra pressure applied. With the increase of reaction time, the FL emission was red
shifted (Fig. 1). The obtained solution containing the QDs was then concentrated by

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reducing the volume to 10 mL, mixed with the same volume of ethanol and then
centrifuged at 8000 rpm for 15 min. Dark red powder was obtained at the bottom of the
solution, which was then collected and dissolved in water.

Fig.1

2.4. Synthesis of QD@MOF

For our method, CdTe QDs wrapped inside Zn2camph2bipy[18] (MOF) structures
synthesized with Zn(NO3)2 and D-camphoric acid were employed as an example to

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demonstrate our idea. The intrinsic structure of D-camphoric acid leads to its easy
bending, which is conducive to forming an enantioselective interface due to an easily

distorted pattern of secondary building unit (SBU) [19] (Fig. 2). The MOF precursors

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were prepared by mixing 0.2 mmol Zn(NO3)26H2O, 0.2 mmol D-camphoric acid and

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0.1 mmol 4, 4-dipyridyl in 40 mL DMF. Subsequently, 1 mL of 0.1 mM QDs was

added in and the solution was placed in the microwave reactor, and heated at 110 oC for

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150 min. Then, light red powder crystals could be observed. After cool down to room
temperature, the obtained red powder was washed several times with DMF and

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ultrapure water.

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Fig. 2

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3. Results and discussion

Compared with previous work about the synthesis of QD@MOF composites [16, 20], a
simple synthesis procedure with less time was developed. Small and homogenouslyQD@MOF

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sized

particles

were

obtained,

and

cheaper

dispersant

of

dimethylformamide (DMF) instead of N,N-diethylformamide [16] was used.

Three pairs of enantiomers were added into the same QD@MOF suspension,
respectively, with only L-tartaric acid causing complete QD quenching, which
demonstrates both size and shape selectivity of the MOF. Furthermore, different
mixtures composed of D- and L-tartaric acids were tested as well, with quenching extent
increasing with the enantiomeric excess percentage (e.e.%). Moreover, it has been
reported that possible interferents such as some metal ions [21] or small molecules [22]
could not cause any obvious QD quenching, although some of them can diffuse into the

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MOF cavities based on their size, so it can be expected that the proposed method would
have practical utility.

The QD@MOF started to grow due to high affinity between the carboxyl group of

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MPA and the Zn-rich metal centres, which was conducive to organized adsorption of D-

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camphoric acid, formation of SBUs, and the ultimate embedding of the QDs within the
formed MOF framework [23]. The obtained QD@MOF particles appeared light red,

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which were thoroughly rinsed with DMF and water. Moreover, no obvious change in
FL signals of the QDs was seen upon the addition of any reactant, which demonstrates

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that the QDs kept stable all through the synthesis process of the QD@MOF.
In Fig. 3a&3b, it can be obviously seen that the QDs (dark spots with similar size)

homogeneously disperse inside the framework based on the transmission electron

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microscope (TEM) images of the QD@MOF, while no similar dark spots were

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observed in the TEM image of the MOF (Fig. 3c). It should also be mentioned that
Yang et al. [24] lately showed the TEM images of ZnO QDs inside porous carbon,
which looked very similar to those in Fig. 3d, while QDs (Fig. 3e) on the surface look

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different, showing clear lattice lines that images of the QD@MOF do not have.
Moreover, according to the spectra of powder X-ray diffraction (PXRD) (Fig. 4), the
dominating peaks of the MOF were consistent with previously reported [13], which
also remained in the spectra of the QD@MOF regardless of some emerging peaks of
the QDs. This demonstrates that the chiral topology structure of the MOF was well
retained even with the QDs caged inside.

Fig. 3
Fig. 4

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The obtained QD@MOF particles were homogeneously dispersed in DMF to prepare a

suspension with a density of 60 g/mL, which appeared red (Fig. 5a). For the

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suspension, with excitation at 365 nm, two emission bands were obtained at 463 nm

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(MOF) and 615 nm (QD), which are significantly blue shifted compared to that of
MOF (472 nm) and QD (643 nm), respectively (Fig. 6). This blue shift relates to the

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increase of the band gap correlated to QD particle size (quantum-size effect) [25]. 10
L of 5 mg/mL of each of six enantiomers (D- and L-tartaric acid, D- and L-dimethyl

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tartrate, D- and L-mandelic acid) in DMF was added into 1 mL of the afore-mentioned
suspension. After 4 h, only L-tartaric acid caused the colour change from red to blue

(Fig. 5a), while the others did not cause any obvious colour change at all. The

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phenomena highly suggest that the QD@MOF can be employed for enantioselective

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sensing of tartaric acid. Furthermore, eleven tartaric acid solutions of varied e.e.% were
added into eleven same QD@MOF suspension, one for each. After 4 h, it can be
observed that the colour of the suspensions changed from red to blue (inset of Fig. 7) as

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e. e.% increased from -100% to 100% due to different QD quenching extents, and each
specific tartaric acid gave a unique appearance. Moreover, several different dispersants
were tested, with DMF giving the best result. The phenomena indicate that the proposed
QD@MOF-based visual enantioselective sensing method can not only accomplish fast
qualification of specific enantiomer but also provide useful information for preliminary
quantification.

Fig. 5
Fig. 6

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Fig. 7
In order to validate the chiral recognition of the QD@MOF, several experiments based

on FL measurements were performed. It should be noted that once molecules with

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similar size to MOF cavity diffuse in, they are very easy to be stuck inside the

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framework. Accordingly, motions (torsional displacements, vibrations, etc.) of SBUs

are inhibited, nonradiative decay was slowed and the fraction of excited species for

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radiative decay was increased, all of which can cause FL intensity of MOF increased
[26]. Moreover, from Fig. 8, it can be seen that even 12 h after the addition of L-tartaric

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acid, the MOF structure was well maintained because the FL signal of the MOF stayed
high and the wavelength of the MOF peak did not change. Or else, FL would be

quenched if the MOF structure were destroyed. As far as our experiments are concerned,

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DMF might act as a collisional quencher [27], and upon the replacement of DMF by

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any enantiomer diffusing in, the quenching effect might be eliminated, which can also
result in the increase of FL intensity of the MOF. For the FL experiments performed,
firstly, the QD quenching was studied by adding each enantiomer into 1 mL of 0.1 mM

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QD solution (without the MOF). The QDs were quenched immediately and the FL
intensity of the QD solution decreased by about 95% (Fig. 5b) except D- and Ldimethyl tartrate. Secondly, D- and L-tartaric acid, and D- and L-mandelic acid was
added into the QD@MOF suspension, respectively. On one hand, the addition of Dand L-mandelic acid did not cause obvious change in FL intensity of even after 12 h
(Fig. 8), most probably because it was difficult for them to diffuse into the framework
based on size selectivity of the MOF. On the other hand, significant difference was
observed in the FL signal change after the addition of D- and L-tartaric acid,
respectively. FL intensity of the QDs decreased sharply less than 0.5 h after the addition

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of L-tartaric acid (Fig. 5c), while the decrease of FL intensity of the QDs was much less
even 4 h after the addition of D-tartaric acid (Fig. 5d). The mostly possible explanation

is that L-tartaric acid could diffuse faster and more easily into the MOF and quench the

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QDs caged in the frameworks than D-tartaric acid based on chiral selectivity of the

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MOF. Thirdly, with the increase of L-tartaric acid concentration (Fig. 9) or e.e.% of
tartaric acid (Fig. 7), FL intensity of the MOF increased and QD decreased in a linear

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fashion, respectively, which illustrates that the proposed method is applicable for
quantification of the enatiomers, even without preliminary separation. Fourthly, D-

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dimethyl tartrate and L-dimethyl tartrate, the according ester enantiomers of D- and Ltartaric acid, were tested as well. The change of FL intensity of the MOF caused by the

addition of L-dimethyl tartrate was much more than D-dimethyl tartrate (Fig. 8) with

Fig. 8
Fig. 9

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the same concentration, which further validates the enantioselectivity of the MOF.

Conclusion and Perspective

A new method was proposed herein to accomplish visual enantioselective determination
by employing QD@MOF as the sensing platform for the first time. Zn2camph2bipy
MOF and CdTe QD were chosen as the model MOF and QD, respectively. A simple
synthesis procedure was used, with small and homogeneously sized QD@MOF
particles obtained. No further modification or functionalization of sensing particles was
needed as previously reported concerning visual enantioselective sensing. The proposed
method is proved to be applicable for fast and facile qualification and preliminary

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quantification of enantiomers, without any analytical instrument needed. Moreover, the

application of this method could be expanded to enantioselective determination of other

enantiomers. First, one specific MOF has been proved to be able to accomplish the

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chiral separation for quite a few pairs of enantiomers, with varied mobile phase

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employed [14b]. Accordingly, it is expected to be feasible that by using varied

dispersant for our proposed method, one specific MOF could be enabled to recognize

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more than one pair of enatiomers which can cause QD quenching. Second, the catalogue
of MOF materials with various chiral topology is growing fast, and some of them have

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demonstrated chiral recognition to specific enantiomer. This makes it highly possible

that more pairs of enantiomers which can cause QD quenching would be distinguished,

as long as the right MOF is found or prepared. In short, the proposed strategy herein

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will have good perspective for visual enantioselective sensing in the future.

Acknowledgements

We acknowledge the financial support from National Natural Science Foundation of

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China (No. 21205083), Sichuan Bureau of Science and Technology (11DXYB353SF027) and Sichuan University (No. 2011SCU11070), and assistance from our Analytical
& Testing Centre for SEM, TEM and PXRD data.

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Figures

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Fig.1 Normalized CdTe QD (QD) FL emission spectra at different reaction time ranging

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from 1 min to 60 min.

Fig.2 The secondary building units of the Zn2camph2bipy (MOF). The pink balls stand
for Zn atoms, the sky blue balls stand for O atoms, and the gray balls stand for C atoms.
H atoms are omitted. The figure is drawn with the Diamond software (version 3.2i,
Crystal Impact GbR, Bonn, Germany).

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Fig. 3 TEM image of the QD@MOF (a, b and d), the MOF (c) and the QDs (e), as well

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as scanning electron microscope image of the QD@MOF (f). Scale bar: 20 nm for (a),

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10 nm for (b) and (c), 2 nm for (d) and (e), and 100 nm for (f).

Fig. 4 PXRD spectra of the synthesized MOF (black) and the QD@MOF (green). The
red bars were stimulated based on the according CheckCIF file of the MOF.

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Fig. 5 (a) Time evolution of UV-excited (292 nm) QD@MOF fluorescent photographs
with injection of L-tartaric acid; (b) Time evolution of QD percentage (%) FL intensity
with the injection of tartaric acid; (c, d) 3D time-resolved evolution of normalized FL

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intensity of the QD@MOF after the injection of L-tartaric acid (c) and D-tartaric acid

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(d).

Fig.6 FL emission spectra of the MOF (blue), the QD (red) and the QD@MOF (black), excited at
365 nm.

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Fig. 7 FL spectra, FL intensity (inset above) and appearance (inset below) of

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QD@MOF suspension 4 h after adding different mixtures of D- and L-tartaric acid.

Fig. 8 FL spectra of the QD@MOF 12 h after the addition of D- and L-mandelic acid;

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D- and L-tartaric acid; and D- and L-dimethyl tartrate.

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Fig. 9 FL spectra of the QD@MOF suspension 4 h after adding L-tartaric acid with
different concentrations (top), and the calibration plot of the FL intensity of the MOF
(middle) and the QD (bottom) changing with the increase of L-tartaric acid
concentration.

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Highlights
Combining size and shape selectivity of MOF and sensing of QD quenching for visual
enantioselective sensing;
A simple synthesis procedure with much less reaction time for small and
homogenously-sized QD@MOF particles;
Direct and convenient for visual enantioselective sensing.

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