Page 3 of 4
Journal Name
ChemComm
ARTICLE
DOI: 10.1039/C5CC03406J
Fig. 4 Intermolecular interactions (a) before and (b) after the oxidation reaction
simulated with Materials Studio 7
Conclusions
This simple multiꢀformyl phenol/amine system is highly
Since the sensing is an oxidation process, the reactivity of TFP- efficient, sensitive, photoꢀstable and selective, leading to new
should be related to the electron cloud distribution especially fluorescent probes for peroxide explosive vapour. The
for its HOMO level. Materials Studio was used for dynamics sensitivity of TFP-I is obtained to be 0.1 ppt for H O and 0.2
I
2
2
(
Forcite plus) and orbitals (DMol3) calculation, using GGAꢀ ppb for TATP, with excellent selectivity towards interference
BLYP as the DFTꢀmethod and COMPASS II vapour including H O. The substitution group and aromatic unit
dynamics)/Dreilding (orbitals) as the force field. As shown in will significantly influence the sensing process suggesting a
2
(
Fig. 3. The HOMO level of ionized molecule TFP-I is ꢀ1.37 eV further structure modification could afford a more efficient
while the neuter molecule TFP is ꢀ6.04 eV. Therefore, the peroxide vapour sensor for onꢀsite, quick and sensitive safety
HOMO level is elevated significantly, which makes it easier to check. Furthermore, the idea of utilizing a reaction product to
be oxidized. With the cyclic voltammetry data, the oxidizing strengthen the interaction between the probe and the analytes
potential of TFP is 2.3 V (HOMO ꢀ5.72 eV) while the opened a new way for the fluorescent probe design.
oxidizing potential of TFP-I is 1.0 V (HOMO ꢀ4.42 eV), so This work is supported by NSFC (No. 61325001, 21273267,
that TFP-I actually shows a better response to oxidants. And 61321492, 51473182). We’d also like to express our thanks to
also based on the results, the band gap is decreased from TFP Mr. Pengcheng Xu for IR measurement and helpful discussions.
to TFP-I resulting in a red shifted absorption and emission.
Actually, the high sensing efficiency is more than a simple
oxidation reaction. The formation of carboxylic products could
Notes and references
a
ShanghaiTech University, 319 Yueyang Road, Shanghai 200031, China
State Key Lab of Transducer Technology, Shanghai Institute of
b
Microsystem and Information Technology, Chinese Academy of
Sciences, Changning Road 865, Shanghai 200050, China.
increase the adsorption capacity of the sensing film to H O2
2
vapour and hence enhance the quenching efficiency. To
interpret it with calculation, crystal cells with periodic
boundary conditions are used to place TFP-I (Fig. 4a) or TFP-
O3 (Fig. 4b) and H O molecules. A large difference of the
Fax: +86ꢀ21ꢀ62511070ꢀ8934; Tel: +86ꢀ21ꢀ62511070ꢀ8967.
†
Electronic Supplementary Information (ESI) available: [general
2
2
materials, methods and the details]. See DOI: 10.1039/b000000x/
References:
stabilized states was found after a same dynamics simulation.
Three more H O ꢀrelated hydrogen bonds formed in the TFP-
2
2
1
2
3
4
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6
2
2
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