Triaza-cryptand and method of determining an alkali ion

• US 6,211,359 B1
• Filed: 08/17/1999
• Issued: 04/03/2001
• Est. Priority Date: 08/17/1999
• Status: Expired due to Term

• Current Assignee: AVL Medical Instruments
• Original Assignee: AVL Medical Instruments
• Inventors: Mortellaro, Mark Alan, He, Huarui, Leiner, Marco Jean Pierre
• Primary Examiner(s): Shah, Mukund J.
• Assistant Examiner(s): Sripada, Pavanaram K
• Application Number:
  US09/375,366
• Time in Patent Office: 595 Days
• Field of Search: 540/467, 540/468, 540/469, 436/79, 436/172
• US Class Current: 540/469
• CPC Class Codes: C07D 498/08 Bridged systems
• CPC Class Codes: C07F 5/022 without C-boron linkages
• CPC Class Codes: G01N 31/22 using chemical indicators G01N31/02 takes precedence
• CPC Class Codes: G01N 33/84 involving inorganic compounds or pH

Abstract

The invention relates to a triaza-cryptand of the general Formula I

wherein

a is selected from the group consisting of 0 and 1,

b and c independently are selected from the group consisting of 0 and 1, with the proviso that not both of b and c are 0,

d is selected from the group consisting of 1, 2 and 3,

e and f independently are selected from the group consisting of 0 and 1, with the proviso that not both of e and f are 0,

R₁ and R₂ are either hydrogen or form an alkyl(C₁-C₄) benzene ring or an alkoxy(C₁C₄) benzene ring together with C₁ and C₂, wherein C₂ is the para position,

R₃ and R₂ are either hydrogen or form an alkyl(C₁-C₄) benzene ring or an alkoxy(C₁-C₄) benzene ring together with C₃ and C₄, wherein C₃ is the para position,

R₅ and R₆ are either hydrogen or form a benzene ring or a naphtalene ring together with C₅ and C₆,

R₇ and R₈ are either hydrogen or form an alkyl(C₁-C₄) benzene ring or an alkoxy(C₁-C₄) benzene ring together with C₇ and C₈, wherein C₈ is the para position,

R₉ and R₁₀ are either hydrogen or form an alkyl(C₁-C₄) benzene ring or an alkoxy(C₁-C₄) benzene ring together with C₉ and C₁₀, wherein C₉ is the para position,

X is a luminophoric moiety in ortho, para or meta position with respect to the nitrogen and m is selected from the group consisting of 0, 1 and 2.

The triaza-cryptand of the invention is useful as a luminescence indicator for alkali ions.

Claims

1. A triaza-cryptand of the general Formula I

wherein

a is selected from the group consisting of 0 and 1,

b and c independently are selected from the group consisting of 0 and 1, with the proviso that not both of b and c are 0,

d is selected from the group consisting of 1, 2 and 3,

e and f independently are selected from the group consisting of 0 and 1, with the proviso that not both of e and f are 0,

R₁ and R₂ are either hydrogen or form an alkyl(C₁-C₄) benzene ring or an alkoxy(C ₁-C₄) benzene ring together with C₁ and C₂, wherein C₂ is the para position,

R₃ and R₄ are either hydrogen or form an alkyl(C₁-C₄) benzene ring or an alkoxy(C₁-C₄) benzene ring together with C₃ and C₄, wherein C₃ is the para position,

R₅ and R₆ are either hydrogen or form a benzene ring or a naphtalene ring together with C₅ and C₆,

R₇ and R₈ are either hydrogen or form an alkyl(C₁-C₄) benzene ring or an alkoxy(C₁-C₄) benzene ring together with C₇ and C₈, wherein C₈ is the para position,

R₉ and R₁₀ are either hydrogen or form an alkyl(C₁-C₄) benzene ring or an alkoxy(C₁-C₄) benzene ring together with C₉ and C₁₀, wherein C₉ is the para position,

X is a luminophoric moiety in ortho, para or meta position with respect to the nitrogen and m is selected from the group consisting of 0, 1 and 2.

2. A triaza-cryptand according to claim 1, wherein the luminophoric moiety X is selected from the group consisting of

an aminonaphthalimide group having the general Formula II

 

wherein at least one of R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ is an —

NH-group through which X is bound to the group —

(CH₂)_m— and

the remaining groups and R₁₇ independently are selected from the group consisting of hydrogen, a lipophilic group, a hydrophilic group and a reactive group for coupling to a polymer,

and

a xanthenone group having the general formula III

 

wherein m=0 and at least one of R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ represents a chemical bond through which X is bound directly to the ionophoric moiety and the remaining groups are each selected from the group consisting of —

OH, —

OR₂₆, wherein R₂₆ is a hydrophilic or a lipophilic group, —

O—

R₂₇—

G, wherein R₂₇ is a hydrophilic or a lipophilic group and G is a reactive group for coupling to a polymer, and —

(CH₂)_n—

COOH, wherein n is a number between 0 and 17,

and

a compound having the general Formula IV

 

wherein at least one of R₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃ und R₃₄ represents a chemical bond through which X is bound to the group —

(CH₂)_m— and

the remaining groups independently are selected from the group consisting of hydrogen, a lipophilic group, a hydrophilic group and a reactive group for coupling to a polymer or a biomolecule, or R₂₉ forms an aromatic ring system together with R₃₀ and R₃₃ forms an aromatic ring system together with R₃₄,

and

a luminescent metal ligand complex.

3. A triaza-cryptand according to claim 1 or 2, wherein each of the three nitrogens of the cryptand is bound to at least one aryl group.

4. A triaza-cryptand according to claim 3, wherein

a=1, b=1, c=1, d=2, e=1, f=1,

R₃, R₄, R₅, R₆, R₇ and R₈ are hydrogen,

R₁ and R₂ form a toluene ring together with C₁ and C₂, wherein C₂ is the para position, and

R₉ and R₁₀ form a toluene ring together with C₉ and C₁₀, wherein C₉ is the para position.

5. A triaza-cryptand according to claim 3, wherein

a=0, b=1, c=1, d=1, e=0, f=1,

R₃, R₄, R₅ and R₆ are hydrogen,

R₁ and R₂ form a toluene ring together with C₁ and C₂, wherein C₂ is the para position, and

R₉ and R₁₀ form a toluene ring together with C₉ and C₁₀, wherein C₉ is the para position.

6. A method of determining an alkali ion in a sample comprising the steps of:

providing a compound having a luminophoric moiety and an ionophoric moiety

reacting the ionophoric moiety with the alkali ion present in the sample, wherein the luminophoric moiety changes its luminescence properties,

measuring the luminescence, and

determining the presence of the alkali ion in the sample utilizing the measured luminescence,

wherein the compound is a triaza-cryptand according to claim 1.

7. A method according to claim 6, wherein the sample has a pH of above 6,5 and the compound is a triaza-cryptand according to claim 3.

8. A method according to claim 6 for determining potassium ions.

9. A method according to claim 8, wherein the compound is a triaza-cryptand according to claim 4.

10. A method according to claim 6 or 7 for determining sodium ions, wherein the compound is a triaza-cryptand according to claim 5.

11. A method according to claim 6, wherein the relative luminescence intensity of the luminophore-ionophore in contact with the ions of the sample is measured and the concentration of the alkali ion is determined utilizing the measured luminescence by a method comprising the steps of

calibrating the luminophore-ionophore in a calibration medium, wherein the relative luminescence intensity Sm_M of the luminophore-ionophore fully saturated with the analyte alkali ion M is determined according to Equation 8 and

determining the concentration cM of the analyte alkali ion M in the sample according to Equation 7.

12. A method according to claim 6, wherein the time-dependent luminescence intensity of the luminophore-ionophore in contact with the ions of the sample is measured after switching off the excitation light and the concentration of the alkali ion is determined utilizing the measured time-dependent luminescence by determining the concentration cM of the analyte alkali ion M in the sample according to Equation 10 and the ratio A_LM/A_L is determined according to Equation 9.

13. An optical sensor for determining alkali ions in a sample, which sensor has a matrix comprising a compound having a luminophoric moiety and an ionophoric moiety, wherein the compound is a triaza-cryptand according to claim 1.