Fluoroionophores and their use in optical ion sensors

Details Fluoroionophores and their use in optical ion sensors Fluoroionophores and their use in optical ion sensors

1999-02-08

2003-06-10

Soderquist, Arlen (Department: 1743)

Chemical apparatus and process disinfecting, deodorizing, preser

Analyzer, structured indicator, or manipulative laboratory...

Calorimeter

C422S051000, C422S082050, C422S082060, C422S082070, C422S082080, C436S073000, C436S079000, C436S172000

Reexamination Certificate

active

06576192

ABSTRACT:

The present invention relates to fluoroionophores containing a fluorophore covalently bound to calix[4]arene via a bridging group and to processes for their preparation. The invention relates also to a) a sensor for determining sodium ions especially in aqueous solutions, which sensor comprises the fluoroionophores in an active layer; b) a method for the qualitative or quantitative determination of sodium ions, especially in aqueous solutions, using the optical sensor; and c) a composition comprising fluoroionophores and polymers.
The optical determination of ions has recently gained greater importance, the presence or concentration of ions being measured, for example, by means of a change in the absorption or fluorescence of a suitable dye. The sensors, also called optrodes, generally consist of a transparent support material and an active layer. The active layer normally comprises a transparent hydrophobic polymer and a lipophilic plasticiser for the purpose of obtaining adequate diffusion of the ions and adequate solubility of the active components. Active components are a specific ionophore as a complexing agent for ions, a counterion for maintaining electrical neutrality, and an indicator substance which, as a result of a chemical change or a physical change in the environment, emits a measurable optical signal. The disadvantages of many such optical sensors are that their response times are too long, they are pH-dependent, their long-term stability is too low for multiple usage and their sensitivities are too low.
The response times may be shortened by covalent linkage of ionophore and fluorophore to form so-called fluoroionophores. Such fluoroionophores are known from WO 89/00997 and U.S. Pat. No. 4,367,072.
In
J. Mater.Chem
. 4(1), (1994), pp. 145-151, Perez-Jimenez et al. describe two novel fluoroionophores that comprise 4 anthracene units covalently bound to calix[4]arene via an amide or ester bond. Disadvantageous fluorescence-quenching effects and lower sensitivity and selectivity as a result of steric hindrance may occur as a result of the close adjacency of the four anthracene units in the molecule.
It has now, surprisingly, been found that calix[4]arenes that comprise only a fluorophore covalently bound already exhibit a high degree of sensitivity and selectivity and are excellently suitable for detecting sodium. It has also, surprisingly, been found that it is possible to bind selectively only a fluorophore covalently to calix[4]arenes, the selectivity of the ionophore being retained. The spacing between the fluorophore and the ionophore can unexpectedly be varied within a wide range by means of the bridging group, without the sensitivity being adversely affected. The ion affinity, which is a necessary precondition for operation as a sensor, is virtually unaltered as a result of the modifications to the calixarene.
The invention accordingly relates firstly to fluoroionophores of formula (I)
wherein
R
06
is H or substituted or unsubstituted C
1
-C
20
alkyl,
R
6
is H or substituted or unsubstituted C
1
-C
30
alkyl or C
1
-C
30
alkoxy,
R
1
is a bridging group, and
F is a residue of a fluorophore.
R
06
is especially linear or branched C
1
-C
12
alkyl, more especially linear or branched C
1
-C
8
alkyl.
Examples of alkyl are methyl, ethyl and the position isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.
In a preferred embodiment, R
06
is H or C
1
-C
4
alkyl.
More especially R
06
is tertiary butyl or ethyl.
R
6
is especially linear or branched C
1
-C
10
alkyl, more especially linear or branched C
1
-C
4
alkyl.
Examples of alkyl are methyl, ethyl and the position isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.
In a preferred embodiment, R
6
is H or C
1
-C
4
alkyl.
More especially R
6
is tertiary butyl.
The bridging group R
1
may contain in the chain from 1 to 30 atoms, preferably from 1 to 20 atoms and especially from 1 to 12 atoms, selected from the group C, O, S and N. The bridging group is preferably a hydrocarbon radical that may be interrupted by one or more hetero atoms from the group O, S and N. For adequate intramolecular interaction between fluorophore and ionophore in the same molecule it may be expedient to select a short bridging group, for example a bridging group having from 1 to 6, preferably from 1 to 4, atoms in the chain.
The bridging group R
1
may correspond to formula (II)
—X
1
—(R
3
)
r
—X
2
—  (II)
wherein X
1
is —O— or —NR
5
,
X
2
is a direct bond or is selected from the groups —O—, —S—, —NR
5
—, —C(O)—O—, —O—C(O)—,
—O—C(O)—O—, —SO
2
—O—, —O—SO
2
—, —O—SO
2
—O—, —NR
5
—C(O)—, —C(O)—NR
5
—, —NR
5
—C(O)—O—,
—O—C(O)—NR
5
—, —NR
5
—C(O)—NR
5
—, —NR
5
SO
2
—, —SO
2
—NR
5
—, —NR
5
—SO
2
—O—, —O—SO
2
NR
5
— and
—NR
5
SO
2
—NR
5
—,
R
5
is H or C
1
-C
30
alkyl, C
5
- or C
6
-cycloalkyl, C
5
- or C
6
-cycloalkylmethyl or -ethyl, phenyl,
benzyl or 1-phenyleth-2-yl,
R
3
is a divalent bridging group,
r is 0 or 1, with the proviso that r is 1 when X
2
is one of the mentioned groups.
When R
5
is alkyl it has preferably from 1 to 6 carbon atoms and especially from 1 to 4 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, butyl, hexyl and octyl. When R
5
is cycloalkyl it is preferably cyclohexyl, and when R
5
is cycloalkylmethyl it is preferably cyclohexylmethyl. In a preferred embodiment, R
5
is H or C
1
-C
4
alkyl.
The divalent bridging group R
3
is preferably a hydrocarbon radical having preferably from 1 to 30 carbon atoms, more preferably from 1 to 18 carbon atoms, especially from 1 to 12 carbon atoms and more especially from 1 to 8 carbon atoms, and is unsubstituted or mono- or poly-substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy or by ═O. The hydrocarbon radical may also be interrupted one or more times by hetero atoms selected from the group —O—, —S— and —NR
5
— wherein R
5
is preferably H or C
1
-C
4
alkyl.
The divalent bridging group R
3
may be, for example, C
1
-C
20
alkylene, preferably C
2
-C
12
alkylene, which may be linear or branched. Examples include methylene, ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1 ,4-butylene, pentylene, hexylene, octylene, dodecylene, tetradecylene, hexadecylene and octadecylene.
The divalent bridging group R
3
may be, for example, polyoxaalkylene having from 2 to 12, especially from 2 to 6, and more especially from 2 to 4, oxaalkylene units and from 2 to 4, preferably 2 or 3, carbon atoms in the alkylene radical. R
3
is especially polyoxaethylene or polyoxapropylene having from 2 to 6 oxaalkylene units.
The divalent bridging group R
3
may be, for example, C
5
-C
12
-, especially C
5
-C
8
- and more especially C
5
- or C
6
-cycloalkyl, such as, for example cyclopentylene, cyclohexylene, cyclooctylene or cyclododecylene.
The divalent bridging group R
3
may be, for example, C
5
-C
12
-, especially C
5
-C
8
- and more especially C
5
- or C
6
-cycloalkyl-C
1
-C
12
- or preferably —C
1
-C
4
-alkyl. Examples include cyclopentyl-C
n
H
2n
— and cyclohexyl-C
n
H
2n
—, wherein n is from 1 to 4. -Cyclohexyl-CH
2
— is especially preferred.
The divalent bridging group R
3
may be, for example, C
5
-C
12
-, especially C
5
-C
8
- and more especially C
5
- or C
6
-cycloalkyl-(C
1
-C
12
alkyl)
2
- or preferably C
1
-C
4
alkyl)
2
. Examples include cyclopentyl-(C
n
H
2n
—)
2
and cyclohexyl-(C
n
H
2n
—)
2
, wherein n is from 1 to 4. —CH
2
-Cyclohexyl-CH
2
— is especially preferred.
The divalent bridging group R
3
may be, for example, C
6
-C
14
arylene, especially C
6
-C
10
-arylene, for example naphthylene or especially phenylene.
The divalent bridging group R
3
may be, for example, C
7
-C
20
aralkylene, especially C
7
-C
12
-aralkylene. Arylene-C
n
H
2n
— wherein arylene is naphthylene or especially phenylene and n is from 1 to 4 is preferred. Examples are benzylene and phenylethylene.
The divalent bridging group R
3
may be, for example, arylene-(C
n
H
2n
—)
2
— wherein arylene is preferably naphthylene or especially phenylene and n is from 1 to 4. Examples include xylylene- and pheny

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