Analytica Chimica Acta 494 (2003) 71–80

Fluorescence and room temperature phosphorescence of

6-bromo-2-naphthol in ␤-cyclodextrin solution and its
selective molecular recognition for cyclohexane
Yan-Qiang Zhai a , Shu-Zhen Zhang b , Jian-Wei Xie b,∗ , Chang-Song Liu c
a Department of Chemistry, Luliang Higher College, Lishi, Shanxi 033000, PR China
b Beijing Institute of Pharmacology and Toxicology, No. 27 Taiping Road, Beijing 100850, PR China
c Department of Chemistry, Shanxi University, Taiyuan 030006, PR China

Received 7 April 2003; accepted 11 July 2003

Abstract
The room temperature phosphorescence (RTP) and fluorescence behavior of 6-bromo-2-naphthol (BN) in water and
␤-cyclodextrin (␤-CD) aerated aqueous solution was investigated. The study of fluorescence behavior at different pH values
indicated that three kinds of species of BN (protonated, uncharged and anionic species) formed 1:1 inclusion complexes
with ␤-CD, and RTP and fluorescence emission depended on the pH of the solution. The inclusion complex constants were
430 ± 25 l mol−1 (pH 1.80), 840 ± 25 l mol−1 (pH 5.80), 1850 ± 75 l mol−1 (pH 11.50), respectively. Experimental results
elucidated that RTP of the BN/␤-CD/cyclohexane solution came from the protonated and uncharged species of BN, but not
from the anionic species, though the inclusion constant of the anionic species of BN with ␤-CD was larger than that of the
other two species of BN Selective molecular recognition of BN/␤-CD as an RTP sensor for 28 small organic molecules was
studied, it was shown that BN/␤-CD could be develop as a new RTP sensor with high selectivity molecular recognition ability
for cyclohexane.
© 2003 Elsevier B.V. All rights reserved.
Keywords: 6-Bromo-2-naphthol; ␤-Cyclodextrin; Fluorescence; Room temperature phosphorescence; Molecular recognition; Cyclohexane

1. Introduction cent sensors for various small organic molecules such

Natural and artificial synthesized supramolecules is
one of the hot topics in recent years. Cyclodextrin as
a natural host has been extensively applied in many
fields such as pharmacy, food, mimic enzyme and
chromatographic separation [1,2]. Many investigations
were focused on designing and synthesizing all kinds
of modified cyclodextrins [3–5] as selective fluores-
∗ Corresponding author. Tel.: +86-10-6693-1649;
fax: +86-10-6821-1656.
E-mail address: xiejw@nic.bmi.ac.cn (J.-W. Xie).
as aliphatic alcohols [6,7], aliphatic amines [8], bile
acids [9], sugars [10] and steroids [11], etc. Some in-
fluencing factors including the size, shape, and polarity
of the guest molecules for selective molecular recogni-
tion of modified cyclodextrins have been discussed in
detail. Fluorescence of twisted intramolecular charge
transfer (TICT) form p-(dimethylamino)benzoyl
(DMAB) modified cyclodextrins was also studied in
an attempt to recognize some small organic molecules
by Hamasaki et al. [7,12]. In contrast, study of
molecular recognition based on room temperature
phosphorescence (RTP) has been rare, because of the

0003-2670/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0003-2670(03)00877-8
72 Y.-Q. Zhai et al. / Analytica Chimica Acta 494 (2003) 71–80
severe conditions requested for RTP emission. Up to
now, only a few kinds of RTP sensors such as oxygen
[13–15] and pH [16] sensors were studied. However,
RTP possesses some remarkable advantages such as
fewer interferences, longer emission wavelength and
high selectivity. Therefore, developing a new RTP
sensor for molecular recognition has great signifi-
cance in both theory and practical application.
RTP emission is normally observed in organized
media, such as micelles [17] or cyclodextrin [18–20]
or on solid substrates [21] under oxygen-removal
conditions but sometimes RTP emission was easily
observed without oxygen removal. For example, RTP
emission from acenaphthene and other phosphors
was still observed in aerated ␤-CD solution, though
the intensity of RTP was decreased to some extent
[22]. It was well known that the RTP of naphtha-
lene, naphthol [23] and their derivatives including ␣-
bromonaphthalene [24–27] and 1-bromo-2-naphthol
[28] were substantially enhanced when they formed
inclusion compounds with cyclodextrin in aerated so-
lutions. Another interesting example of cyclodextrin-
induced RTP in air-saturated aqueous solution was
reported by Nocera and co-workers [29]. Intense RTP
emission was observed by appending bromonaph-
thalene to the secondary hydroxyl group of ␤-CD,
which easily formed an intramolecular complex by
inclusion of the attached bromonaphthalene into the
cavity of ␤-CD. We have reported much stronger
RTP emission from ␣-bromonaphthalene/␤-CD/
cyclohexane than that from ␣-bromonapbthalene/␤-
CD/cyclohexanol and ␣-bromonaphthalene/␤-CD/2-
methylcyclohexanol without oxygen removal when
the RTP intensity was measured immediately after the
solution was prepared. In addition, the stronger inclu-
sion ability of cyclohexane with ␣-bromonaphthalene/
␤-CD than that of cyclohexanol was proved by mea-
suring the inclusion constant [30].
6-Bromo-2-naphthol (BN) in aerated ␣-cyclodextrin
(␣-CD) solution was reported to be a phosphol
by Hamai and Kudou [31–33] and some other re-
searchers [34,35], which proposed the formation of a
2:1 ␣-CD-BN inclusion complex. ␣-CD decreased not
only the oxygen-quenching rate but also the other de-
activation rates of the triplet state of BN. A BN/␤-CD/
cyclohexane ternary complex had been reported by
Escandar and Boldrini [36]. Room temperature of
BN in micelles was also investigated [37]. Unfortu-
nately, the fluorescence and RTP behavior as well
as the molecular recognition ability of the BN/␤-CD
complex were not studied in-depth.
In the present paper, the effect of pH, molecular
species of BN, and polarity of the media on the flu-
orescence and RTP properties of the complex is ex-
tensively investigated. A strong molecular recognition
ability for cyclohexane with high selectivity was de-
veloped based on the BN/␤-CD inclusion complex
without oxygen removal.
2. Experimental
2.1. Apparatus
RTP and fluorescence spectra and intensity were
recorded and measured on a Hitachi model F-4010
spectrofluorometer. RTP lifetime measurement was
carried out on a Perkin-Elmer LS-50B spectrofluo-
rometer with the following instrumental parameters:
scintillation count, 1; cyclic number, 40; gate width,
5 ms; delayed time, 0.0–15 ms.
The RTP lifetime was calculated according to the
following equation:
In It = In I0 − kt
where It , and I0 are the intensities at a delay time of t
and 0 ms, respectively; ln It versus t was plotted and a
straight line produced. The RTP lifetime was obtained
from the negative reciprocal of the slope of the line
(−1/k).
pH values were measured with a pHM-64 Research
pH Meter, Radiometer A/S Copenhagen), The pH
of the solution was adjusted with H2 SO4 or NaOH
solution.
2.2. Reagents
␤-CD was purchased from Shanghai Chemical
Reagents Purchasing and Supply Station, purified by
recrystallization three times from boiling water and
dried in a vacuum desiccator. BN was obtained from
Baker Chemicals and used without further purification.
␣-Bromonaphthalene was purchased from Shanghai
Reagent Factory and purified by reduced-pressure
distillation. Cyclohexane was of analytical-reagent
grade and obtained from the Beijing Reagent Factory.
 Y.-Q. Zhai et al. / Analytica Chimica Acta 494 (2003) 71–80
Other reagents were of analytical-reagent grade or
purified by distillation. Water was doubly distilled in
a sub-boiling still.
3. Results and discussion
3.1. RTP of β-CD/BN/cyclohexane inclusion
complex
BN in water and ␤-CD solution emitted fluores-
cence but no RTP. After adding traces of cyclohexane
(0.06% (v/v)) to ␤-CD/BN solution, strong RTP emis-
sion was observed, as shown in Fig. 1. Some other
small organic molecules such as a variety of alco-
hols with cyclic, straight and branched chains, halo-
genated compounds, and alkyl and aryl compounds
could not induce RTP emission of ␤-CD/BN solution.
It indicated that a rigid ternary inclusion complex was
formed only between BN, ␤-CD and cyclohexane.
Factors such as the concentration of cyclohex-
ane, and ␤-CD as well as the pH of the solution
affected significantly the intensity and RTP lifetime
of the ␤-CD/BN/cyclohexane host-guest inclusion
complex.
Fig. 1. The emission spectra of 1.00 × 10−4 mol l−1 6-bromo-2-naphthol in (a) water, (b) 5.00 × 10−5 mol l−1 ␤-CD, (c) 5.00 × 10−5 mol l−1
␤-CD and 5.55 × 10−5 mol l−1 cyclohexane.
73
3.1.1. Concentration of cyclohexane
RTP intensity of BN in ␤-CD solution increased
with addition of increasing amounts of cyclohexane,
and approached its maximum when only 0.06% (v/v)
of cyclohexane had been added. At the same time, the
RTP lifetime also increased from 2.0 to 6.3 ms. These
results revealed that the presence of cyclohexane de-
creased the deactivation rates of the triplet state of BN
due to the quenchers and oxygen in the solution and
thus increased the RTP lifetime.
3.1.2. Concentration of β-CD
The RTP intensity and lifetime of ␤-CD/BN/cyclo-
hexane solution increased with increasing concentra-
tion of ␤-CD, until it reached a maximum. On further
increasing the concentration of ␤-CD, the RTP inten-
sity and lifetime of the inclusion complex decreased
somewhat because of the dynamic quenching process
caused by inclusion complexation [19].
3.1.3. pH
Fig. 2 demonstrates the effect of pH on the RTP
intensity and lifetime of the ␤-CD/BN/cyclohexane
ternary host–guest inclusion complex. With increase
in pH of the solution, the RTP intensity decreased
74 Y.-Q. Zhai et al. / Analytica Chimica Acta 494 (2003) 71–80
Fig. 2. Effect of pH on (a) RTP intensity and (b) lifetime of ␤-CD/6-bromo-2-naphthol/cyclohexane.
gradually and finally approached zero when the pH
>11.0.
BN can exist as three kinds of species: a proto-
nated species, an uncharged molecule and an anionic
species (pKa of BN ground state is 9.2 [31]). When
pH was low enough, the protonated and uncharged
species were the major components. With increase
in pH, the concentration of the anionic species in-
creased. When the pH had increased to 11.0, BN in
the solution existed almost only as the anionic species;
under these conditions on RTP signal was observed.
It implied that the RTP of the solution came from the
protonated and uncharged species of BN, but not from
the anionic species. The RTP lifetime also increased
and then decreased with increase in pH. When pH of
the solution was low, BN was protonated to a certain
extent, which made the inclusion complexation with
␤-CD difficult mainly because hydrogen bond forma-
tion of protonated BN with ␤-CD was weak and led
to a shorter RTP lifetime. RTP lifetime with increas-
ing pH of the solution, which confirmed that the rigid
ternary inclusion complex (BN/␤-CD/cyclohexane)
was formed. Further increasing pH of the solution,
the species of BN gradually changed to the anion
RTP emission decreased and the RTP lifetime became
shorter.
3.2. Effect of pH on fluorescence emission
behavior of BN
Fig. 3 illustrates the effect of pH on the fluorescence
emission behavior of BN in the absence of ␤-CD.
From the inserted figure, it can be observed that the
fluorescence emission wavelength of uncharged BN
was near 360 nm, and that of the anionic species was
clearly at about 420 nm when the pH was >6.0. From
curves (a) and (b) in Fig. 3, the wavelength of fluores-
cence of both species and anionic species was slightly
red-shifted with increase in pH. This is because the
enhancement of conjugation between the lone electron
pair of –OH or –O−1 and the naphthalene ring due to
the attenuation of protonation with increasing pH [38].
From curve (c) in Fig. 3, the fluorescence inten-
sity decreased dramatically with the increase of pH
in the low pH range. Combined with the increase of
RTP lifetimes in the same pH range (see curve (b) in
Fig. 2), it should be a reasonable interpretation that
these phenomena resulted from the protonation of BN
and the effect of the heavy atom (Br− ). On increas-
ing the pH from 5.8 to 8.4, the fluorescence intensity
increased slightly. Further increasing the pH, the fluo-
rescence intensity of the uncharged species decreased
rapidly, accompanied by an increase in fluorescence
 Y.-Q. Zhai et al. / Analytica Chimica Acta 494 (2003) 71–80 75

Fig. 3. Effect of pH on fluorescence emission wavelength of (a) uncharged species, (b) anionic species, and on intensity of (c) uncharged
species, (d) anionic species of 6-bromo-2-naphthol in the absence of ␤-CD. Inset fluorescence emission spectra of 6-bromo-2-napththol in
solutions of pH (from (a) to (h)): 6.0, 7.3, 8.3, 8.8, 9.3, 9.4, 9.8, 10.4 in the absence of ␤-CD.

intensity of the anionic species the Influence of pH of the uncharged species blue-shifted with increase
on the fluorescence of BN in the presence of ␤-CD is in pH (curve (a) in Fig. 4). It was suggested that
shown in Fig. 4. Different from the absence of ␤-CD BN be shielded in the cavity of ␤-CD, which pre-
(see Fig. 3), the fluorescence emission wavelength vented the protonation of BN to a certain extent, the

Fig. 4. As Fig. 3 in the presence of ␤-CD. Inset fluorescence emission spectra of 6-bromo-2-napthol in solutions of pH (from (a) to (h)):
5.9, 6.4, 8.0, 8.8, 9.1, 9.4, 10.3, 11.4 in the presence of ␤-CD.
76 Y.-Q. Zhai et al. / Analytica Chimica Acta 494 (2003) 71–80
complexation between ␤-CD and BN was enhanced
with increase in pH, and placed BN in a more hy-
drophobic microenvironment. When the pH increased
to 8.0, the fluorescence emission from the anionic
species was detectable though it was relatively weak,
as shown in inset in Fig. 4.
Another different result in the presence of ␤-CD
was that the fluorescence intensity of the uncharged
species decreased more slowly with increasing acid-
ity, indicating again that the protonation of BN was
shielded by the presence of ␤-CD. When the pH in-
creased from 5.9 to 8.8, the fluorescence intensity from
the uncharged species increased dramatically. On fur-
ther increasing the pH of the solution, the fluorescence
intensity of the uncharged species decreased rapidly,
accompanied by an increase in the fluorescence inten-
sity of the anionic species.
The third difference between the presence and ab-
sence of ␤-CD was that much more intense fluores-
cence of BN was observed in the presence of ␤-CD
when the pH was in the range 5.8–11.0 This provides
powerful evidence for inclusion complex formation
between ␤-CD and the uncharged or anionic species
of BN. The inclusion complex constant of BN/␤-CD
as well as the stoichiometric ratios were studied later.
In a general way, the fluorescence emission spectra
of many fluorescent compounds, especially for those
with acidic basic groups on aromatic rings, usually de-
pends on pH, polarity and hydrogen bonding ability
of the medium [38]. In order to obtain enough infor-
mation on the effect of media with different properties
on the fluorescence emission as well as the inclusion
complexation between BN and ␤-CD, the fluorescence
emission spectra were recorded at different pH values
in water, ␤-CD/water, and ␤-CD/water/cyclohexane.
λmax values for fluorescence emission of BN are listed
in Table 1.
Table 1
Wavelengths (nm) of maximum fluorescence emission of BN at
different pH in different media
Medium pH
1.90 5.80 10.40
Water 357 365 422
␤-CD/water 366 360 416
␤-CD/water/cyclohexane – – 405
As seen in Table 1, λmax for the fluorescence emis-
sion of the uncharged (pH 5.8) and anionic species (pH
10.4) of BN were blue-shifted on addition of ␤-CD
and cyclohexane. These results confirmed that binary
or ternary inclusion complexes are formed by the in-
clusion complexation of ␤-CD with the uncharged and
anionic species, which made the microenvironment of
BN more hydrophobic in the cavity of ␤-CD. This was
the characteristics of a ␲–␲∗ transition, that is, the flu-
orescence wavelength was blue-shifted with increase
in hydrophobicity of the microenvironment. λmax for
the fluorescence emission of BN was red-shifted from
357 to 366 nm when its medium changed from water
to a mixture of water and ␤-CD (pH 1.9) due to the
shielding action from protonation of BN caused by
inclusion in the ␤-CD. The λmax for the fluorescence
emission of BN in water at pH 5.8 (365 nm) and in
a ␤-CD/water medium pH 1.9 (366 nm) were almost
identical, which further indicated that the protonation
of BN was weakened in the presence of ␤-CD when
the pH was low (1.9). It implied that the BN species
extruded from the ␤-CD cavity into the bulk water en-
vironment in acidic solution more than that in neutral
and weakly basic solutions, Therefore a smaller inclu-
sion constant of the complex should be expected in
acidic media.
3.3. Study of the acid–base properties of ground
state and excited state BN
Generally, the acid–base properties of a ground state
and excited state molecule could be acquired by inves-
tigating the fluorescence behavior in some media of
different pH. Because most of the proton transfer reac-
tions are fast in polar solvents, a Brønsted acid–basic
reaction could occur in the lifetime of a singlet state
of aromatic compounds [38]. For instance the pKa for
the ground state of 2-naphthol is 9.5 [39]. However,
the fluorescence emission from the anionic species of
2-naphthol was still observed when the pH of the solu-
tion was much below 9.5, implying that the acidity for
the excited state of 2-naphthol was stronger than that
of its ground state. This was consistent with the re-
ported pKa∗ of 3.05 for the excited state of 2-naphthol
[39]. We investigated the acid–base properties for the
ground state and excited state of BN by the simi-
lar method. It was demonstrated that the fluorescence
emission of BN anionic species was observed when
 Y.-Q. Zhai et al. / Analytica Chimica Acta 494 (2003) 71–80
the pH was ≥6.0 (see inset in Fig. 3) in the absence
of ␤-CD, while in the presence of ␤-CD, fluorescence
from anionic species of BN was observed when pH
was ≥8.0 (see inset in Fig. 4). Although we could
not obtain the precise value of dissociation constant
(pKa∗ ) of its excited state, this results suggested that
the apparent pKa∗ value of BN in the presence of
␤-CD was nearly the same as the pKa (9.2) [31] of
its ground state, and that the excited state of BN in
water was more acidic than that in ␤-CD solution,
probably because the dissociation of the excited state
of BN was weakened due to inclusion complexation
by ␤-CD.
In summary, a study on the RTP and fluorescence
behavior of BN in different pH solution revealed that
both uncharged and anionic species of BN formed an
inclusion complex with ␤-CD, and the inclusion com-
plexation was weak when the pH was low because
of the protonation of BN. Strong RTP was induced
in BN/␤-CD by adding a trace amount of cyclohex-
ane, the RTP emission came from protonated and
uncharged species of BN, but not from its anionic
species. The acidity for the excited state of BN in
␤-CD solution was much weaker than that in water,
which was identical with the acidity for the ground
state (pKa 9.2) of BN.
3.4. Stoichiometric ratio and inclusion complex
constants of BN/β-CD and BN/β-CD/cyclohexane
To obtain more accurate information on the inclu-
sion complexation between BN and ␤-CD and con-
firm our explanation about all the experimental results
mentioned above, stoichiometric ratios and inclusion
complex constants were determined.
The Benesi–Hildebrand method [40] was applied to
acquire the stoichiometric ratios and inclusion com-
plex constants of BN/␤-CD. Fitting data 1/(F − F0 )
versus 1/[␤-CD] gave a satisfactory straight line,
which revealed that the stoichiometric ratio of
BN/␤-CD was 1:1. An equilibrium method was also
used to study the stoichiometric ratio and the above
result was verified. According to the slope and in-
tercept of the Benesi–Hildebrand plots, the inclusion
complex constants of BN/␤-CD at different pH values
were calculated and are displayed in Table 2.
Data listed in Table 2 clearly demonstrate that
the inclusion complex constant was much smaller
77
Table 2
Inclusion complex constants of BN/␤-CD at different pH values
pH Species of BN Inclusion complex
constants (l mol−1 )
1.80 Protonated species 430 ± 25
5.80 Uncharged species 840 ± 25
1850 ± 75
11.50 Anionic species
at low pH, which indicated that ␤-CD had weak
inclusion ability with the protonated species of
BN (430 ± 25 l mol−1 ). It had much stronger in-
clusion ability with the uncharged species of BN
(840 ± 25 l mol−1 ) and the strongest inclusion
ability for anionic species (1850 ± 75 l mol−1 ).
A comparison of the complex of BN/␤-CD with
2-naphthol/␤-CD at different pH, the greater inclu-
sion constant for BN/␤-CD (840 ± 25 l mol−1 at pH
5.8, and 590 ± 50 l mol−1 for 2-naphthol/␤-CD at
pH 6.5 [14], and 1850 ± 75 l mol−1 at pH 11.50 and
180 ± 30 l mol−1 for 2-naphthol/␤-CD at pH 1.7 [39])
indicated that the hydrophobic bromine atom in BN
led to stronger inclusion by ␤-CD.
Similarly, the inclusion constant of ␤-CD/BN/
cyclohexane (1:1:1) [26,30] was also calculated by the
Benesi–Hildebrand method. A much larger inclusion
complex constant for BN/␤-CD (2360 l mol−1 ) for the
cyclohexane ternary complex than for the BN/␤-CD
binary inclusion complex (840 ± 25 l mol−1 ). It con-
firmed our explanation that the inclusion complexing
ability of ␤-CD was greatly enhanced by the addition
of cyclohexane.
3.5. Selective molecular recognition of BN/β-CD
The potential application of BN/␤-CD as a RTP sen-
sor for small organic molecule recognition was stud-
ied. Twenty-eight small organic compounds (listed in
Table 3) were added to BN/␤-CD solution and the RTP
intensity was measured in each instance. The results
are illustrated in Fig. 5 in order to compare the se-
lectivity for molecular recognition between ␣-bromo-
naphthalene/␤-CD and BN/␤-CD as RTP sensors.
Although the amount of other organic molecules
added was larger than that of cyclohexane, Table 3
clearly shows that the increase in RTP signal
in BN/␤-CD solution was weak (<10%), except
for tert-butyl chloride (27.4%), xylylaminoethanol
(20.7%) and benzene (11.1%). In contrast, adding
78 Y.-Q. Zhai et al. / Analytica Chimica Acta 494 (2003) 71–80

Table 3
Comparison of selective recognition ability of BN/␤-CD with that of ␣-monaphthalene/␤-CD
Serial Small organic molecule ␣-Bromonaphthalene/␤-CD 6-Bromo-2-naphthol/␤-CD
number
Content Normalized RTP Content Normalized RTP
(% (v/v))a intensityb (% (v/v))a intensityb
1 Methanol 1 1.1 1 0.7
2 Ethanol 1 4.7 1 0.7
3 Isopropanol 1 1.8 1 0.7
4 n-Butanol 1 10.6 1 0.7
5 Isobutanol 1 2.0 1 0.7
6 tert-Butanol 1 50.8 1 0.7
7 n-Pentanol 1 6.5 1 0.8
8 Isoamyl alcohol 1 24.2 1 0.8
9 dl-sec-Amyl alcohol 1 72.7 0.5 10.1
10 tert-Amyl alcohol 1 91.5 1 6.4
11 Cyclohexanol 1 96.0 1 1.1
12 n-Heptanol 1 3.8 1 0.7
13 Benzoic alcohol 0.2 1.8 0.2 9.3
14 Glycol 1 0.8 1 0.8
15 Cyclohexane 0.02 100.0 0.06 100.0
16 ␣-Propylene glycol 1 1.0 1 0.8
17 Xylylaminoethanol 1 75.8 1 20.8
18 Dichloromethane 0.1 22.2 0.5 6.0
19 Chloroform 0.1 36.4 0.5 5.8
20 1,2-Dichloroethane 0.1 51.6 0.5 9.7
21 Tetrabromoethane 0.1 3.2 0.5 1.5
22 tert-Butyl chloride 0.1 72.4 0.5 27.4
23 n-Hexane 0.1 11.5 0.5 5.2
24 n-Hexane 0.1 9.6 0.5 5.1
25 Benzene 0.1 12.0 0.1 11.1
26 Toluene 0.1 4.2 0.1 4.2
27 Dimethylbenzene 0.1 9.1 0.1 6.2
28 Acetophenone 0.1 2.2 0.1 2.1
a The concentration used to achieve the strongest RTP intensity.
b Normalized RTP intensity (BN/␤-CD/cyclohexane = 100).

these small organic molecules to ␣-bromonaphthalene/
␤-CD solution, only 14 organic compounds caused a
RTP signal increase <10%. Thus, many small organic
compounds interfered with the selective recognition of
cyclohexane in ␣-bromonaphthalene/␤-CD solution,
but the situation in BN/␤-CD solution was greatly
improved. A study showed that the 3σ limit of detec-
tion (LOD) for cyclohexane was 1.51 × 10−5 mol l−1 .
Therefore, it could be applied as an RTP de-
tector for cyclohexane with high selectivity and
sensitivity.
The selective molecular recognition of BN/␤-CD
solution for cyclohexane depended not only on the
size, shape and lipophilic–hydrophobic properties of
cyclohexane, but also on the flexibility of cyclohexane.
The study showed that little or no RTP was induced
when other molecules of similar size such as cyclohex-
anol, benzene, toluene alcohol and acetophenone were
added to BN/␤-CD solution. Some other molecules
with similar lipophilic–hydrophobic properties such
as n-hexane, n-heptane, and benzene also could not
induce strong RTP. Even some halogenated alkanes
as heavy atom perturbes could not induce strong
RTR. Only cyclohexane could induce intense RTP in
BN/␤-CD solution. It indicated that cyclohexane had
the best special complementarity with BN/␤-CD, the
ternary inclusion ␤-CD/BN/cyclohexane effectively
removed the oxygen in the cavity of ␤-CD, and intense
RTP signal was observed without oxygen-removal
procedure.
 Y.-Q. Zhai et al. / Analytica Chimica Acta 494 (2003) 71–80
Fig. 5. Comparison of relative RTP intensity between ␣-bromonaphthalene/␤-CD and 6-bromo-2-naphthol/␤-CD after adding small organic
molecules. The serial numbers of the organic molecules are shown in Table 3.
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